Ethylene polymer

ABSTRACT

An ethylene-based polymer which is a copolymer obtained from ethylene and a C3 to C10α-olefin and satisfies the following requirements (i), (ii), (iii) and (iv) simultaneously provides a blow-molded product and an extrusion-molded product excellent in moldability, mechanical strength and outward appearance. 
         (i) melt flow rate [MFR 2  (g/10 min)] under a loading of 2.16 kg at 190° C. is in the range of 0.01 to 10,    (ii) melt tension [MT (g)] and the above melt flow rate [MFR 2  (g/10 min)] satisfy the following relationship: MT≧3.2×MFR 2   −0.55 , (iii) an activation energy [Ea] of fluidization is less than 30 (KJ/mol), and (iv) swell ratio is 1.36 or more. The ethylene-based polymer of the invention is preferably produced by copolymerizing ethylene with a C3 to C10 α-olefin, in the presence of a solid catalyst carrying, on (C) a solid carrier, a mixed transition metal compound consisting of (A1) a group 4 transition metal compound containing a specific salicyl aldimine ligand and (A2) a group 4 transition metal compound containing a specific cyclopentadienyl ligand and (B) at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound reacting with the transition metal compound to form an ion pair.

TECHNICAL FIELD

The present invention relates to a novel ethylene-based polymer, apolymerization catalyst and a polymerization method for producing theethylene-based polymer, and use of the ethylene-based polymer.Specifically, the present invention relates to (1) an ethylene-basedpolymer satisfying specific properties, (2) a method of producing theethylene-based polymer by using a polymerization catalyst carrying, on asolid carrier, at least one transition metal compound containing asalicyl aldimine ligand and at least one transition metal compoundcontaining a cyclopentadienyl ligand, and at least one compound selectedfrom an organometallic compound, an organoaluminum oxy compound, and acompound reacting with the transition metal compound to form an ionpair, and (3) use of the ethylene-based polymer in blow-molded products,pipes etc.

BACKGROUND ART

Polyolefins such as polyethylene and polypropylene are clean materialsconsisting of carbon and hydrogen not detriment to the environment, andare excellent in processing moldability and physical properties. Becauseof these characteristics, these materials have been used in a widevariety of fields in automobiles, electric instrument parts, foodpackages, drink/cosmetic/medical containers, civil engineeringmaterials, and agricultural materials etc. In recent years, however,there are various demands for physical properties of polyolefin, andpolyolefin having various characteristics are desired. Furtherimprovement in productivity is also desired. Particularly when blowmolding or sheet molding is conducted, melt tension (hereinafterabbreviated sometimes as MT) and swell ratio are desired to be high.

As ethylene-based polymers excellent in these physical properties,polyethylene produced by a high-pressure process and polyethyleneobtained by a Cr-based Philips type catalyst are known, but there is alarge amount of long chains and branched chains therein, and thusrigidity and impact strength are lowered. Further, regulation of theamount of long chains and branched chains and introduction of α-olefincomonomers are difficult, so there is limit to physical properties whichcan be attained. Further, such high-pressure polyethylene has theproblem of high fluidization activating energy as a measure oftemperature dependence for generating resin fluidization at the time ofmolding.

Conventionally, a Zeigler type titanium-based catalyst comprising atitanium-based compound and an organoaluminum compound is well known asa polymerization catalyst for producing an ethylene polymer and anethylene-based polymer such as an ethylene/α-olefin copolymer. In recentyears, a metallocene-based catalyst comprising a metallocene compoundhaving a cyclopentadienyl group and an organoaluminum oxy compound(aluminoxane) comes to be known as a catalyst by which an olefin polymercan be produced with a high polymerization activity, and recently, anovel catalyst system comprising a transition metal compound having aligand of diimine structure has also been proposed (see WO96/23010A2).Recently, a metallocene compound having a cyclopentadienyl grouppreferable as a catalyst for producing an ethylene-based polymer withnarrow compositional distribution has also been proposed as a novelolefin polymerization catalyst by the present applicant inWO2004/029062A1. Further, the present applicant has also proposed, inJapanese Patent Application Laid-Open No. 11-3151.09 and EP0874005A1, atransition metal compound containing a salicyl aldimine ligand. Thetransition metal compound containing a salicyl aldimine ligand ischaracterized in that it is easily synthesized, has a high ethylenepolymerization performance, and can regulate polymerization performancesuch as molecular weight, copolymerizability etc. by changing thestructure of the ligand.

Ethylene-based polymers obtained by using these polymerization catalystsare excellent in rigidity and impact strength as compared with theabove-mentioned high-pressure process polyethylene or Cr-based catalystproduct, but cannot be said to be satisfactory in respect of MT andswell ratio, so there is room for improvement.

Some proposes have been made to solve these problems for theabove-mentioned catalysts. For example, Japanese Patent ApplicationLaid-Open No. 7-278221 describes that an ethylene-based polymerexcellent in MT and swell ratio is obtained by combination of a specificTi compound, a liquid Mg compound and a compound having an etherlinkage. In this case, however, the swell ratio is 1.35 or less, whichcannot be said to be sufficiently high. The present inventors havedisclosed a process for producing a long-chain and branchedchain-containing polyolefin by using a combination of specifictransition metal compounds in Japanese Patent Application Laid-Open No.2002-105132. In this case, however, the activation energy offluidization is increased by introduction of long chains and branchedchains, but the effect on improvement of MT is low.

In view of the process for production of polyolefin including thepolyethylene-based polymer, high-density polyethylene has been producedgenerally by slurry polymerization, generally in a low-pressure processusing a Ziegler type catalyst. When high-density polyethylene having anarbitrary molecular-weight distribution, among the above high-densitypolyethylenes, is produced for the purpose of regulating moldability andphysical properties, the polymerization is conducted in multistage, andusually the molecular weight and density of a polymer formed in eachstage is regulated in the polymerization. Specifically, thepolymerization is constituted of a multistage slurry polymerizationprocess consisting of a low-molecular-weight polyethylene polymerizationstep and a high-molecular-weight polyethylene polymerization step, butin such multistage process, there remain problems to be solved withrespect to the process and cost because of troublesome operation due tothe multistage process and necessity for use of a large amount ofhydrogen in the process of formation of low-molecular-weightpolyethylene.

The present inventors made extensive studies for improvement of melttension and rationalization of the process for polyolefin by themultistage polymerization method, and as a result, they found polyolefinexhibiting excellent melt tension and low activation energy offluidization and overcoming the problems of the conventional resin byregulating the length and amount of long chains and branched chains byusing a specific olefin polymerization catalyst.

DISCLOSURE OF INVENTION

The ethylene-based polymer of the present invention is a copolymerobtained from ethylene and a C3 to C10 α-olefin and satisfying thefollowing requirements (i), (ii), (iii) and (iv) simultaneously:

(i) melt flow rate [MFR₂ (g/10 min)] under a loading of 2.16 kg. at 190°C. is in the range of 0.01 to 10,

(ii) melt tension [MT (g)] and the above melt flow rate [MFR₂ (g/10min)] satisfy the following relationship:MT≧3.2×MFR ₂ ^(−0.55)

(iii) the activation energy [Ea] of fluidization is less than 30(KJ/mol), and

(iv) swell ratio is 1.36 or more.

The ethylene-based polymer of the present invention is preferablyobtained by copolymerizing ethylene with a C3 to C10 α-olefin, in thepresence of a solid catalyst component carrying on (C) a solid carrier:

(A1) a group 4 transition metal compound represented by the generalformula [I] below,

(A2) a group 4 transition metal compound represented by the generalformula [II] below, and

(B) at least one compound selected from:

-   -   (b-1) an organometallic compound,    -   (b-2) an organoaluminum oxy compound, and.    -   (b-3) a compound reacting with the transition metal compound        (A1) or (A2) to form an ion pair,        where the meanings of various symbols will be described in        detail in “Best Mode for Carrying Out the Invention” described        later.        where the meanings of various symbols will be described in        detail in “Best Mode for Carrying Out the Invention” described        later.

Further, the present invention relates to a blow-molded productcomprising the ethylene-based polymer described above. Theethylene-based polymer is applied preferably to a blow-molded product,particularly an oil drum, a large container, a large gasoline tank, alarge industrial chemical can or a large bottle container.

Further, the present invention relates to a pipe or a pipe jointcomprising the ethylene-based polymer described above.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a graph in which melt tension and MFR₂ values ofethylene-based polymers obtained in the Examples and ComparativeExamples are plotted.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the ethylene-based polymer of the present invention andapplications thereof are specifically described.

The ethylene-based polymer of the present invention is a copolymerobtained from ethylene and a C3 to C10 α-olefin and satisfying thefollowing requirements (i), (ii), (iii) and (iv) simultaneously:

(i) melt flow rate [MFR₂ (g/10 min)] under a loading of 2.16 kg at 190°C. is in the range of 0.01 to 10,

(ii) melt tension [MT (g)] and the above melt flow rate [MFR₂ (g/10min)] satisfy the following inequation:MT≧3.2×MFR ₂ ^(−0.55)   (Eq-1)

(iii) the activation energy [Ea] of fluidization is less than 30(KJ/mol), and

(iv) swell ratio is 1.36 or more.

The ethylene-based polymer of the present invention is an ethylenehomopolymer or a copolymer obtained from ethylene and a C3 to C10α-olefin; that is, the ethylene-based polymer contains anethylene-derived structural unit as an essential component and furthercontains a C3 to C10 α-olefin-derived structural unit. The C3 to C10α-olefin may be one kind of olefin or two or more different kinds ofolefins. The C3 to C10α-olefin (hereinafter referred to sometimes as“α-olefin”) includes, for example, propylene, 1-butene, 1-pentene,3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,1-octene and 1-decene. In the present invention, the ethylene-basedpolymer preferably contains a structural unit derived from at least onemember selected from 1-hexene, 4-methyl-1-pentene and 1-octene, morepreferably a structural unit derived from 1-hexene. The ethylene-basedpolymer of the present invention is an ethylene-based polymer in whichthe C3 to C10 α-olefin-derived structural unit is contained in an amountof usually 0 to 5.0 mol %, preferably 0.05 to 1.0 mol %, more preferably0.1 to 0.5 mol %.

The ethylene-based polymer of the present invention is characterized insimultaneously satisfying the requirements (i), (ii), (iii) and (iv)described above. Hereinafter, each requirement is described in detail.

Requirement (i)

The melt flow rate [MFR₂ (g/10 min)] of the ethylene-based polymer ofthe present invention under a loading of 2.16 kg at 190° C. is in therange of 0.01 to 10. The melt flow rate [MFR₂ (g/10min)] is preferablyin the range of 0.01 to 5, more preferably in the range of 0.1 to 5.

Requirement (ii)

One feature of the ethylene-based polymer of the present invention isthat in the above-defined range of melt flow rate [MFR₂ (g/10 min)]under a loading of 2.16 kg, this melt flow rate and melt tension [MT(g)] satisfy the following inequation (Eq-1). The following inequation(Eq-2) is preferably satisfied, and the following inequation (Eq-3) ismore preferably satisfied.MT≧3.2×MFR ₂ ^(−0.55)   (Eq-1)12.0×MFR ₂ ^(−0.55) ≧MT≧3.2×MFR ₂ ^(−0.55)   (Eq-2)8.0×MFR ₂ ^(−0.55) ≧MT≧3.6×MFR ₂ ^(−0.55)   (Eq-3)Requirement (iii)

The fluidization activation energy [Ea] of the ethylene-based polymer ofthe present invention is less than 30 (KJ/mol), preferably 10 to 28(KJ/mol), more preferably 20 to 28 (KJ/mol). When Ea is in this range,the ethylene-based polymer is advantageous in that it is excellent influidity.

Requirement (iv)

The swell ratio of the ethylene-based polymer of the present inventionis 1.36 or more, preferably 1.40 or more. When the swell ratio is inthis range, a product having uniform thickness with less distribution ofthickness can be obtained by blow molding.

The ethylene-based polymer of the present invention preferably satisfiesthe following requirements (v) to (vii) in addition to the requirements(i) to (iv) described above.

Requirement (v)

The density of the ethylene-based polymer of the present invention is inthe range of 910 to 970 (kg/m³), preferably 920 to 970 (kg/m³), morepreferably 930 to 970 (kg/m³)

Requirement (vi)

The intrinsic viscosity [η] of the ethylene-based polymer of the presentinvention is in the range of 1.0 to 5.0 (dl/g), preferably 1.5 to 3.0(dl/g).

Requirement (vii)

The intrinsic viscosity ([η] (dl/g)) and melt flow rate at 190° C. undera loading of 21.6 kg [MFR₂₀ (g/10 min)] of the ethylene-based polymer ofthe present invention satisfy the following inequation (Eq-4),preferably the following inequation (Eq-5):[η]≦1.3 log (MFR ₂₀)+4.35   (Eq-4)−1.3 log (MFR ₂₀)+3.50≦[η]≦−1.3 log (MFR ₂₀)+4.35   (Eq-5)

The melt flow rate [MFR₂₀(g/10 min)]at 190° C. under a loading of 21.6kg is usually in the range of 1 to 100 (g/10 min), preferably 1 to 50(g/10 min), more preferably 2 to 30 (g/10 min).

The ethylene-based polymer of the present invention satisfying the aboverequirements (i) to (iv) and the parameter ranges prescribed preferablyin the above requirements (v) to (vii) can be produced arbitrarily asdesired by using the production conditions in the Examples in thispatent application, or by making a minor change in condition factors, orby blending such resins. The ethylene-based polymer of the presentinvention can be produced as desired, specifically by changing conditionfactors such as structures of the transition metal compounds [I] and[II] used, the carrying ratio, requirements for the catalyst componentsuch as the type of a carrier and a co-catalyst component, as well aspolymerization conditions such as polymerization temperature, the amountof a molecular weight regulator such as coexistent hydrogen, and theamount of a comonomer added. Further, the range of physical propertiescan be enlarged by combination with multistage polymerization.

More specifically, the amount of a long chain and branched chain whichcan be introduced into the polymer can be increased by lowering thepolymerization temperature, by increasing the amount of comonomersadded, or by changing the structure of the transition metal compound [I]used, etc., and in this case, the value of MT tends to be increasedrelatively to the value of MFR, while the value of [η] tends to bedecreased relatively to the value of MFR. The activation energy (Ea) offluidization can be regulated by changing a combination of thetransition metal catalysts. Particularly, when the transition metalcatalysts are a combination of a transition metal compound having thestructure of [I] and a 4 group transition metal compound containing 2cyclopentadienyl skeletons as the ligand wherein the 2 cyclopentadienylskeletons are bound to each other via the group 4 atom, Ea can beregulated to 30 KJ/mol or more.

The ethylene-based polymer of the present invention is obtained bycopolymerizing ethylene with the above-mentioned C3 to C10 α-olefin, inthe presence of a polymerization catalyst carrying on (C) a solidcarrier:

(A1) a group 4 transition metal compound represented by the generalformula [I] below,

(A2) a group 4 transition metal compound represented by the generalformula [II] below, and

(B) at least one compound selected from:

-   -   (b-1) an organometallic compound,    -   (b-2) an organoaluminum oxy compound, and    -   (b-3) a compound reacting with the transition metal compound        (A1) or (A2) to form an ion pair.

Hereinafter, the respective constituent components of the polymerizationcatalyst according to the present invention are described in detail.

(A1) Group 4 transition metal compound represented by the generalformula [I] below

where N . . . M generally shows that the two elements are coordinated,but in the present invention, they may or may not be coordinated.

In the general formula [I], M represents a transition metal atom in thegroup 4 in the periodic table, and is specifically titanium, zirconiumor hafnium, preferably zirconium. m is an integer of 1 to 4, preferably2, and n is a number. satisfying the valence of M, and R¹ to R⁶ may bethe same or different and each represent a hydrogen atom, a halogenatom, a hydrocarbon group, a heterocyclic compound residue, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group, and two or more of these groups may be bound toone another to form a ring.

When m is 2 or more, two of the groups represented by R¹ to R⁶ may bebound to each other provided that R¹s shall not be bound to each other.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n, is 2 or more, a plurality of groupsrepresented by X's may be the same or different, and a plurality ofgroups represented by X's may be bound to one another to form a ring,

Hereinafter, R¹ to R⁶ are specifically described.

The halogen atom includes fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include a C1 to C30,preferably C1 to C20, linear or branched alkyl group such as a methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group,isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexylgroup etc.; a C2 to C30, preferably C2 to C20, linear or branchedalkenyl group such as a vinyl group, allyl group, isopropenyl groupetc.; a C2 to C30, preferably C2 to C20, linear or branched alkynylgroup such as an ethynyl group, propargyl group etc.; a C3 to C30,preferably C3 to C20, saturated cyclic hydrocarbon group such as acyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexylgroup, adamantyl group etc.; a C5 to C30 unsaturated cyclic hydrocarbongroup such as a cyclopentadienyl group, indenyl group, fluorenyl groupetc.; a C6 to C30, preferably C6 to C20, aryl group such as a phenylgroup, naphthyl group, biphenyl group, terphenyl group, phenanthrylgroup, anthracenyl group etc.; and an alkyl-substituted aryl group suchas a tolyl group, iso-propylphenyl group, tert-butylphenyl group,dimethylphenyl group, di-tert-butylphenyl group etc.

The hydrocarbon group may be the one whose hydrogen atom is replaced bya halogen, and examples thereof include a C1 to C30, preferably C1 toC20, halogenated hydrocarbon group such as a trifluoromethyl group,pentafluorophenyl group, chlorophenyl group etc.

The hydrocarbon group may be substituted with other hydrocarbon groups,and examples thereof include an alkyl group substituted with an arylgroup such as benzyl group, cumyl group, 2,2-diphenylethyl group,triphenylmethyl group etc.

The hydrocarbon group may have a heterocyclic compound residue; anoxygen-containing group such as an alkoxy group, aryloxy group, estergroup, ether group, acyl group, carboxyl group, carbonate group, hydroxygroup, peroxy group, carboxylic anhydride group etc.; anitrogen-containing group such as an amino group, imino group, amidegroup, imido group, hydrazino group, hydrazono group, nitro group,nitroso group, cyano group, isocyano group, cyanate group, amidinogroup, diazo group, a group whose amino group is converted into anammonium salt, etc.; a boron-containing group such as a borane diylgroup, borane triyl group, diboranyl group etc.; a sulfur-containinggroup such as a mercapto group, thioester group, dithioester group,alkylthio group, arylthio group, thioacyl group, thioether group,thiocyanate group, isothiocyanate group, sulfone ester group,sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfogroup, sulfonyl group, sulfinyl group, sulphenyl group etc.; aphosphorus-containing group such as a phosphide group, phosphoryl group,thiophosphoryl group, phosphate group etc.; and a silicon-containinggroup, a germanium-containing group or a tin-containing group.

Particularly preferable among these are a C1 to C30, preferably C1 toC20, linear or branched alkyl group such as a methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, isobutyl group,sec-butyl group, tert-butyl group, neopentyl group, n-hexyl group etc.;a C6 to C30, preferably C6 to C20, aryl group such as a phenyl group,naphthyl group, biphenyl group, terphenyl group, phenanthryl group,anthracenyl group etc.; and a substituted aryl group substituted with 1to 5 substituent atoms or groups such as a halogen atom, a C1 to C30,preferably C1 to C20, alkyl group or alkoxy group, a C6 to C30,preferably C6 to C20, aryl group or aryloxy group.

The oxygen-containing group, the nitrogen-containing group, theboron-containing group, the sulfur-containing group and thephosphorus-containing group include the same groups as illustratedabove.

The heterocyclic compound residue includes a nitrogen-containingcompound residue such as pyrrole, pyridine, pyrimidine, quinoline,triazine etc.; an oxygen-containing compound residue such as furan,pyran etc.; and a sulfur-containing compound residue such as thiopheneetc., and these heterocyclic compound residues may be furthersubstituted with a substituent group such as a C1 to C30, preferably C1to C20, substituent groups such as an alkyl group, alkoxy group etc.

The silicon-containing group includes a silyl group, siloxy group,hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxygroup etc., and specific examples include a methyl silyl group, dimethylsilyl group, trimethyl silyl group, ethyl silyl group, diethyl silylgroup, triethyl silyl group, diphenylmethyl silyl group, triphenyl silylgroup, dimethylphenyl silyl group, dimethyl-t-butyl silyl group,dimethyl(pentafluorophenyl) silyl group, etc. Preferable among these area methyl silyl group, dimethyl silyl group, trimethyl silyl group, ethylsilyl group, diethyl silyl group, triethyl silyl group, dimethylphenylsilyl group, triphenyl silyl group, etc. Particularly, a trimethyl silylgroup, triethyl silyl group, triphenyl silyl group, and dimethylphenylsilyl group are preferable. Specifically, the hydrocarbon-substitutedsiloxy group includes a trimethylsiloxy group etc.

The germanium-containing group or the tin-containing group includesthose groups wherein silicon of the above silicon-containing group wasreplaced by germanium or tin.

Two or more groups of R¹ to R⁶, preferably adjacent groups, may be boundto each other to form an aliphatic ring, an aromatic ring, or ahydrocarbon ring containing a heteroatom such as a nitrogen atom, andthese rings may further have a substituent group.

When m is 2 or more, two of the groups represented by R¹ to R⁶may bebound to each other. When m is 2 or more, R¹s, R²S, R³s, R⁴ S, R⁵s orR⁶s may be the same or different.

n is a number satisfying the valence of M, and is specifically aninteger of 0 to 5, preferably 1 to 4, more preferably 1 to 3.

X represents a hydrogen atom, a halogen atom, a hydrocarbon; group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by X's may be the same or different, and a plurality ofgroups represented by X's may be bound to one another to form a ring.

Hereinafter, specific examples are described.

The halogen atom includes fluorine, chlorine, bromine and iodine.

The hydrocarbon group includes the same groups as illustrated above inR¹ to R⁶. Among these, a C1 to C20 hydrocarbon group is preferable.

The heterocyclic compound residue, the oxygen-containing group, thesulfur-containing group and the nitrogen-containing group include thesame groups as illustrated above in R¹ to R⁶.

Specifically, the boron-containing group includes BR₄ where R ishydrogen, an alkyl group, an optionally substituted aryl group, ahalogen atom etc.

Specifically, the phosphorus-containing group includes, but is notlimited to, a trialkylphosphine group such as a trimethylphosphinegroup, tributylphosphine group, tricyclohexylphosphine group etc.; atriarylphosphine group such as a triphenylphosphine group,tritolylphosphine group etc.; a phosphite group (phosphide group) suchas a methylphosphite group, ethylphosphite group, phenylphosphite groupetc.; aphosphonic acid group; andaphosphinic acid group.

The silicon-containing group, the germanium-containing group and thetin-containing group include the same groups as illustrated above in R¹to R⁶.

Specifically, the halogen-containing group includes, but is not limitedto, a fluorine-containing group such as PF₆, BF₄ etc., achlorine-containing group such as ClO₄, SbCl₆ etc., and aniodine-containing group such as IO₄ etc.

Specifically, the aluminum-containing group includes, but is not limitedto, AlR₄ where R represents hydrogen, an alkyl group, an optionallysubstituted aryl group, a halogen atom etc.

When n is 2 or more, a plurality of groups represented by X's may be thesame or different, and a plurality of groups represented by X's may bebound to one another to form a ring.

In the present invention, the group 4 transition metal complexpreferable as the group 4 transition metal compound (A1) represented bythe general formula [I] is represented by the following general formula[III]:

where M represents a transition metal atom in the group 4 in theperiodic table, m represents an integer of 1 to 4, R¹′ is represented bythe general formula [IV] or [V] below, R² to R⁶ may be the same ordifferent and each represent a hydrogen atom, a halogen atom, ahydrocarbon group, a heterocyclic compound residue, an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group, and two or more of these groups may be bound toone another to form a ring, and when m is 2 or more, two of the groupsrepresented by R² to R⁶ may be bound to each other provided that R¹'sshall not be bound to each other, and n is a number satisfying thevalence of M, X represents a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by X's may be the same or different, and a plurality ofgroups represented by X's may be bound to one another to form a ring;

where R_(a) represents a hydrogen atom, an aliphatic hydrocarbon groupor an alicyclic hydrocarbon group, and R_(b) and R_(c) each represent ahydrogen atom or a methyl group and may be the same or different;

where the broken line indicates that two C_(β)s are bound directly toeach other, or two C_(β)s are bound to each other via a C1 or morehydrocarbon group.

R¹′ is an aliphatic hydrocarbon group or alicyclic hydrocarbon grouprepresented by the general formula [IV] or [V], and includes, forexample, C1 to C3 hydrocarbon groups. Specific examples include methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-pentyl, tert-amyl, 1,2-dimethylpropyl, isoamyl, 1-methylbutyl,2-methylbutyl, neopentyl, n-hexyl, 1,3-dimethylbuty, 3,3-dimethylbutyl,n-heptyl, 1-methylhexyl, n-octyl, 1,5-dimethylhexyl, 2-ethylhexyl,1-methylheptyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl,n-tridecyl,n-tetradecyl,n-pentadecyl,n-hexadecyl,n-heptadecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl,cyclododecyl, adamantyl, methylene cyclopropyl, methylene cyclobutyl,methylene cyclopentyl, methylene cyclohexyl, 1-cyclohexylethyl etc.,among which R¹′ is preferably methyl, ethyl, n-propyl, n-hexyl,n-octadecyl, cyclohexyl, cycloheptyl, cyclooctyl,4-tert-butylcyclohexyl, methylene cyclohexyl, isopropyl, 1-methylhexylor 1,5-dimethylhexyl, particularly preferably 4-tert-butylcyclohexyl,methylene cyclohexyl, isopropyl, 1-methylhexyl or 1,5-dimethylhexyl.

As R² to R⁶, R² to R⁶ illustrated in the group 4 transition metalcompound represented by the general formula [I] can be used withoutparticular limitation.

When m is 2 or more, two of the groups represented by R² to R⁶ may bebound to each other. When m is 2 or more, R²s, R³s , R⁴s, R⁵s or R⁶s maybe the same or different.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by X's may be the same or different, and a plurality ofgroups represented by X's may be bound to one another to form a ring.

n is a number satisfying the valence of M, and is specifically aninteger of 0 to 5, preferably 1 to 4, more preferably 1 to 3.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and specifically X illustrated in the group 4transition metal compound represented by the general formula [I] can bementioned. When n is 2 or more, a plurality of groups represented by X'smay be the same or different, and a plurality of groups represented byX's may be bound to one another to form a ring.

As the group 4 transition metal compound represented by the generalformula [I] or [III], two or more different kinds of compounds can beused.

The method of producing the transition metal compound (A1) is notparticularly limited, and the transition metal compound (A1) can beproduced for example by a method described in the present applicant'sJapanese Patent Application Laid-Open No. 11-315109 and EP0874005A1.

Specific examples of the 4 group transition metal compound representedby the general formula [III] include, but are not limited to, thefollowing compounds:

In the above examples, Me represents a methyl group, Et represents anethyl group, ^(t)Bu represents a tert-butyl group, and Ph represents aphenyl group.

In the present invention, the transition metal compounds wherein in theabove compounds, a zirconium metal was replaced by a metal such astitanium or hafnium other than zirconium. (A2) Group 4 transition metalcompound represented by the general formula [II]

The group 4 transition metal compound represented by the general formula[II] in the present invention is the following crosslinked metallocenecompound:

where R⁷ to R²⁰ are selected from hydrogen, a hydrocarbon group and asilicon-containing group, and may be the same or different, adjacentsubstituents R7 to R²⁰ may be bound to each other to form a ring, M is agroup 4 transition metal atom, Y is a group 14 metal atom, Q may beselected in the same or different combination from a halogen, ahydrocarbon group, an anion ligand, and a neutral ligand capable ofcoordination with a lone pair of electrons, and j is an integer of 1 to4.

Specifically, the hydrocarbon group of R⁷ to R²⁰ includes a C1 to C20alkyl group, a C7 to C20 alkyl group, a C6 to C20 aryl group etc.Examples include a methyl group, ethyl group, n-propyl group, isopropylgroup, allyl group, n-butyl group, tert-butyl group, amyl group,n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonylgroup, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group,1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutylgroup, 1,1-dimethyl-2-methylpropyl group,1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexylgroup, cycloheptyl group, cyclooctyl group, norbornyl group, adamantylgroup, phenyl group, naphthyl group, biphenyl group, phenanthryl group,anthracenyl group, benzyl group, cumyl group, methoxy group, ethoxygroup, phenoxy group, N-methylamino group, N,N-dimethylamino group,N-phenylamino group etc.

The silicon-containing group can include a trimethyl silyl group,triethyl silyl group, diphenylmethyl silyl group, dimethylphenyl silylgroup etc.

Mention is also made of a cyclohexyl group, cyclopentyl group, adamantylgroup etc. where R¹⁹ and R²⁰ are bound to each other to form a ring.

In preferable modes of R¹⁹ and R²⁰, at least one of R¹⁹ and R²⁰is anunsubstituted aryl group or a substituted aryl group. In this case, whenthe two are either unsubstituted aryl groups or substituted aryl groups,R¹⁹ and R²⁰ may be the same or different.

88 More specifically, when R¹⁹ and R²⁰are unsubstituted aryl groups orsubstituted aryl groups, mention is made of a C6 to C30, preferably C6to C20, aryl group such as a phenyl group, naphthyl group, biphenylgroup, terphenyl group, phenanthryl group, anthracenyl group etc. and analkyl-substituted aryl group such as a tolyl group, iso-propylphenylgroup, tert-butylphenyl group, ethylphenyl group, dimethylphenyl group,di-tert-butylphenyl group etc. Further examples include a substitutedaryl group substituted with 1 to 5 substituent atoms or groups such as ahalogen atom, a C1 to C30, preferably C1 to C20, alkyl group or alkoxygroup, a C6 to C30, preferably C6 to C20, aryl group or aryloxy group,and a halogen-containing hydrocarbon group such as a chlorophenyl group,dichlorophenyl group, fluorophenyl group, difluorophenyl group,trifluoromethylphenyl group, di(trifluoromethyl)phenyl group etc.

The covalent bonding atom Y for bonding the cyclopentadienyl ligand tothe fluorenyl ligand is the group 14 atom which is a carbon atom, asilicon atom, a germanium atom, analkylene group, a substituted alkylenegroup, a silylene group, a substituted silylene group or the like.Specific examples include, for example, crosslinking moieties consistingof C6 to C20 unsaturated hydrocarbon groups such as —C(C₆H₅)₂—, —C(C₆H₅)(p-CH₃C₆H₅)—, —C(p-CH₃C₆H₅) (p-CH₃C₆H₅)—, —C(tert-BuC₆H₅)(tert-BuC₆H₅)—, —SiC(C₆H₅)₂—, —Si(C₆H₅) (p-CH₃C₆H₅) —, —Si (p-CH₃C₆H₅)(p-CH₃C₆H₅)—, —Si(tert-BuC₆H₅) (tert-BuC₆H₅)— etc.

Q is selected in the same or different combination from a halogen, ahydrocarbon group, an anion ligand, and a neutral ligand capable ofcoordination with a lone pair of electrons. j is an integer of 1 to 4,and when j is 2 or more, Q may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine andiodine, and examples of the hydrocarbon group include those describedabove.

Examples of the anion ligand include an alkoxy group such as methoxy,tert-butoxy, phenoxy etc., a carboxylate group such as acetate, benzoateetc., a sulfonate group such as mesylate, tosylate etc.

Specific examples of the neutral ligand capable of coordination with alone pair include organic phosphorus compounds such as trimethylphosphine, triethyl phosphine, triphenyl phosphine, diphenyl methylphosphine etc., and ethers such as tetrahydrofuran, diethyl ether,dioxane, 1,2-dimethoxyethane etc. At least one of Q's is preferably ahalogen-or an alkyl group.

The group 4 transition metal compounds represented by the generalformula [II] include, but are not limited to, the following examples:

Di(m-tolyl) methylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, di(m-tolyl) methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl) methylene (cyclopentadienyl)(fluorenyl) zirconium dichloride, di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconiumdichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride,di(m-trifluoromethyl-phenyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl). zirconium dichloride, di(m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (fluorenyl)zirconium dichloride, di(p-trifluoromethyl-phenyl) methylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,di(p-trifluoromethyl-phenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride,di(p-trifluoromethyl-phenyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (fluorenyl)zirconium dichloride, di(p-tolyl) methylene (cyclopentadienyl)(2,7-dimethylfluorenyl) zirconium dichloride, di(p-tolyl) methylene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,di(p-isopropylphenyl) methylene (cyclopentadienyl) (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(p-tert-butylphenyl) methylene (cyclopentadienyl) (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl)methylene (cyclopentadienyl) (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dimethyl,cyclopentylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, cyclohexylidene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, adamantylidene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,cyclopentylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)zirconium dichloride, cyclohexylidene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, adamantylidene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,cyclopropylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconiumdichloride, cyclobutylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl)zirconium dichloride, cyclopentylidene (cyclopentadienyl)(3,6-dimethyl-fluorenyl) zirconium dichloride, cyclohexylidene(cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride,cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconiumdichloride, cyclopropylidene (cyclopentadienyl) (3,6-di-tert-fluorenyl)zirconiumdichloride, cyclobutylidene (cyclopentadienyl)(3,6-di-tert-fluorenyl) zirconium dichloride, cyclopentylidene(cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconiumdichloride,cyclohexylidene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconiumdichloride, cycloheptylidene (cyclopentadienyl) (3,6-di-tert-fluorenyl)zirconium dichloride, cyclopropylidene (cyclopentadienyl)(3,6-dicumyl-fluorenyl) zirconium dichloride, cyclobutylidene(cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride,cyclopentylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconiumdichloride, cyclohexylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl)zirconium dichloride, cycloheptylidene (cyclopentadienyl)(3,6-dicumyl-fluorenyl) zirconium aichloride, cyclopropylidene(cyclopentadienyl) (3, 6-di-tert-fluorenyl) zirconium dibromride,cyclobutylidene (cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconiumdibromide, cyclopentylidene (cyclopentadienyl) (3, 6-di-.tert-fluorenyl)zirconium dibromide, cyclohexylidene (cyclopentadienyl)(3,6-di-tert-fluorenyl) zirconium dibromide, cycloheptylidene(cyclopentadienyl) (3,6-di-tert-fluorenyl) zirconiumdibromide,cyclopropylidene (cyclopentadienyl) (2,7-di-tert-fluorenyl) zirconiumdichloride, cycloprobutylidene (cyclopentadienyl)(2,7-di-tert-fluorenyl) zirconium dichloride, cyclopentylidene(cyclopentadienyl) (2,7-di-tert-fluorenyl) zirconium dichloride,cyclohexylidene (cyclopentadienyl) (2,7-di-tert-fluorenyl) zirconiumdichloride, cycloheptylidene (cyclopentadienyl) (2,7-di-tert-fluorenyl)zirconium dichloride, cyclopropylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dichloride, cyclopentylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dichloride, cycloheptylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,cyclopropylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dibromide,cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dibromide, cyclopentylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dibromide,cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dibromide, cycloheptylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dibromide,cyclopropylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dimethyl,cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dimethyl, cyclopentylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dimethyl,cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dimethyl, cycloheptylidene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dimethyl,di-n-butylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,di-n-butylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, di-n-butylmethylene (cyclopentadienyl)(3,6-di-tert-butyl fluorenyl) zirconium dichloride, di-n-butylmethylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconiumdichloride, di-n-butylmethylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, di-n-butylmethylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di-n-butylmethylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,di-n-butylmethylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,diisobutylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, diisobutylmethylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, diisobutyimethylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconiumdichloride., diisobutylmethylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, diisobutylmethylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, diisobutylmethylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,diisobutylmethylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,dibenzylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, dibenzylmethylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconiumdichloride, dibenzylmethylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, dibenzylmethylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, dibenzylmethylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,dibenzylmethylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,diphenethylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, diphenethylmethylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenethylmethylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconiumdichloride, diphenethylmethylene (cyclopentadienyl) (benzofluorenyl)zirconiumdichloride, diphenethylmethylene (cyclopentadienyl)(dibenzofluorenyl) zirconiumdichloride, diphenethylmethylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,diphenethylmethylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,di(benzhydryl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, di(benzhydryl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(benzhydryl)methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(benzhydryl) methylene (cyclopentadienyl)(benzofluorenyl) zirconium dichloride, di(benzhydryl) methylene(cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride,di(benzhydryl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl)zirconium dichloride, di(benzhydryl) methylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di(cumyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,di(cumyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, di(cumyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(cumyl) methylene(cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconiumdichloride, di(cumyl) methylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, di(cumyl) methylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di(cumyl) methylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,di(cumyl) methylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,di(1-phenyl-ethyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, di(1-phenyl-ethyl)methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconiumdichloride, di(1-phenyl-ethyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(1-phenyl-ethyl) methylene (cyclopentadienyl) (dibenzofluorenyl)zirconium dichloride, di(1-phenyl-ethyl) methylene (cyclopentadienyl)(octahydrodibenzofluorenyl) zirconium dichloride, di(1-phenyl-ethyl)methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(cyclohexylmethyl) methylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, di(1-cyclohexyl-ethyl) methylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,di(cyclopentylmethyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(cyclopentylmethyl) methylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, di(cyclopentylmethyl) methylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di(cyclopentylmethyl) methylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,di(cyclopentylmethyl) methylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,di(naphthylmethyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, di(naphthylmethyl)methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconiumdichloride, di(naphthyImethyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(naphthylmethyl) methylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, di(naphthylmethyl) methylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di(naphthylmethyl) methylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,di(naphthylmethyl) methylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,di(biphenylmethyl) methylene (cyclopentadienyl) (fluorenyl) zirconiumdichloride, di (biphenylmethyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, di(biphenylmethyl)methylene-(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconiumdichloride, di(biphenylmethyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(biphenylmethyl) methylene (cyclopentadienyl) (benzofluorenyl)zirconium dichloride, di(biphenylmethyl) methylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di(biphenylmethyl) methylene(cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,di(biphenylmethyl) methylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,dimethylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)zirconium dichloride, dimethylmethylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium-dichloride,dimethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconiumdichloride, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl)zirconium dichloride, dimethylmethylene (cyclopentadienyl)(octahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene(cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconiumdichloride, dimethylsilylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,dimethylsilylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,dimethylsilylene (cyclopentadienyl) (benzofluorenyl) zirconiumdi-chloride, dimethylsilylene (cyclopentadienyl) (dibenzofluorenyl)zirconium dichloride, dimethylsilylene (cyclopentadienyl)(octahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene(cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconiumdichloride, cyclopentylidene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,adamantylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconiumdichloride, dimethylmethylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,di(p-tolyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, diethylmethylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclopentylidene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,cyclohexylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)zirconium dichloride, adamantylidene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylmethylene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,diphenylmethylene (cyclopentadienyly (3,6-di-tert-butylfluorenyl)zirconium dichloride, di(p-tolyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, diethylmethylene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,monophenylmonomethylmethylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,di(p-tolyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl). (3,6-di-tert-butylfluorenyl) zirconium dichloride,di(p-tolyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride,di(p-tolyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)hafnium dichloride., monophenylmonomethylmethylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride,di(p-tolyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,diphenylmethylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl)methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,diphenylmethylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,di(p-tolyl) methylene (cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,monophenylmonomethylmethylene (cyclopentadienyl) (dibenzofluorenyl)zirconium dichloride, diphenylmethylene (cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di(p-tolyl) methylene(cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride,monophenylmonomethylmethylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) hafnium dichloride,diphenylmethylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) hafnium dichloride, di(p-tolyl)methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)hafnium dichloride, monophenylmonomethylmethylene (cyclopentadienyl)(octamethyltetrahydrodibenzofluorenyl) titanium dichloride,diphenylmethylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) titanium dichloride, di(p-tolyl)methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)titanium dichloride, di(p-tolyl) methylene (cyclopentadienyl)(fluorenyl) zirconium dichloride, di(p-tolyl) methylene(cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride,di(p-tert-butylphenyl) methylene (cyclopentadienyl) (fluorenyl)zirconium dichloride, di(p-tert-butylphenyl) methylene(cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,di(p-tert-butylphenyl) methylene (cyclopentadienyl)(2,7-dimethylfluorenyl) zirconium dichloride, di(p-tert-butylphenyl)methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconiumdichloride, di(p-n-butylphenyl) methylene (cyclopentadienyl) (fluorenyl)zirconium dichloride, di(p-n-butylphenyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, di(p-n-butylphenyl)methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconiumdichloride, di(p-n-butylphenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(m-tolyl) methylene(cyclopentadienyl) (fluorenyl) zirconium dichloride, di(m-tolyl)methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconiumdichloride, di(m-tolyl) methylene (cyclopentadienyl)(2,7-dimethylfluorenyl) zirconium dichloride, di(m-tolyl) methylene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride,(p-tolyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconiumdichloride, di(p-isopropylphenyl) methylene (cyclopentadienyl)(fluorenyl) zirconium dichloride, di(p-tert-butylphenyl) methylene(cyclopentadienyl) (fluorenyl) zirconiumdichloride,di(p-tolyl)methylene(cyclopentadienyl) (fluorenyl)zirconium dimethyl,(p-tolyl) (phenyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(p-isopropylphenyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,di(p-tert-butylphenyl) methylene (cyclopentadienyl).(octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di(p-tolyl)methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl)zirconium dimethyl, di(p-tolyl) methylene (cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl)(phenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, di(p-isopropylphenyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride,di(p-tert-butylphenyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, di(p-tolyl) methylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dimethyl,(p-tolyl) (phenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(p-isopropylphenyl)methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconiumdichloride, di(p-tert-butylphenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(p-tolyl) methylene(cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dimethyl,(p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl)zirconium dichloride, (p-tert-butylphenyl) (phenyl) methylene(cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,(p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl)(2,7-dimethylfluorenyl) zirconium dichloride, (p-tert-butylphenyl)(phenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl)zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene(cyclopentadienyl) (fluorenyl) zirconium dichloride, (p-n-ethylphenyl)(phenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene(cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride,(p-n-ethylphenyl) (phenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl)methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,(4-biphenyl) (phenyl) methylene (cyclopentadienyl)(2,7-di-tert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl)methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconiumdichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, di(4-biphenyl)methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,di(4-biphenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl)zirconium dichloride, di(4-biphenyl) methylene (cyclopentadienyl)(2,7-dimethylfluorenyl) zirdonium dichloride, di(4-biphenyl) methylene(cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, orcompounds derived from the above compounds by changing their“cyclopentadienyl” into “(3-tert-butyl-5-methyl-cyclopentadienyl)” or“(3,5-dimethyl-cyclopentadienyl)”, or by changing their zirconium intohafnium, titanium etc.

However, the crosslinked metallocene compound of the present inventionis not limited to the exemplary compounds shown above, and encompassesall compounds satisfying the requirements of the general formula [II].

The crosslinked metallocene compound represented by the general formula[II] in the present invention can be produced by known methods, and theproduction process is not particularly limited. The known productionprocess includes a method in WO01/27174 filed by the present applicant.

In the present invention, the ethylene-based polymer of the presentinvention can also be produced by using the group 4 transition metalcompound (A2′) containing a cyclopentadienyl skeleton as a ligand,besides the group 4 transition metal compound represented by the generalformula [II]. The transition metal compound (A2′) is not particularlylimited, and the metallocene compound preferably used includes., forexample, bis(methylcyclopentadienyl) zirconium dichloride,bis(dimethylcyclopentadienyl) zirconium dichloride,bis(dimethylcyclopentadienyl) zirconium ethoxychloride,:bis.(dimethylcyclopentadienyl) zirconium bis(trifluoromethanesulfonato),bis(ethylcyclopentadienyl) zirconium dichloride,bis(protylcyclopentadienyl) zirconium dichloride,bis(methylpropylcyclopentadienyl) zirconium dichloride, bis(butylcyclopentadienyl) zirconium dichioride,bis(methylbutylcyclopentadienyl) zirconium dichloride,bis(methylbutylcyclopentadienyl) zirconium.bis(trifluoromethanesulfonato), bis(trimethylcyclopentadienyl) zirconiumdichloride, bis(tetramethylcyclopentadienyl) zirconium dichloride,bis(pentamethylcyclopentadienyl) zirconium dichloride,bis(hexylcyclopentadienyl) zirconium dichloride,bis(trimethylsilylcyclopentadienyl) zirconium dichloride., etc.

The metallocene compound (A2′) is preferably a group 4 transition metalcompound containing two cyclopentadienyl skeletons as the ligand whereinthe two cyclopentadienyl skeletons are bound to each other via the group14 atom, more preferably a metallocene compound (A2″) with a chiralstructure having C2 symmetry. Preferable examples of the metallocenecompound (A2″) with a chiral structure having C2 symmetry includerac-ethylene-bis(indenyl) zirconium dichloride,rac-ethylene-bis(tetrahydroindenyl) zirconium dichloride,rac-dimethylsilylene-bis(2,3,5-trimethylcyclopentadienyl) zirconiumdichloride,

rac-dimethylsilylene-bis[1-(4-phenylindenyl)] zirconium dichloride,

rac-dimethylsilylene-bis[1-(2-methyl-4-phenylindenyl)] zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(1-naphthyl)indenyl] zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(2-naphthyl)indenyl] zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(1-anthryl)indenyl]} zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(9-anthryl)indenyl]} zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(9-phenanthryl)inden yl]}zirconium dichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(o-chlorophenyl)inde nyl]}zirconium dichloride,

rac-dimethylsilylene-bis{1-[2-methyl-4-(pentafluorophenyl)indenyl]}zirconium dichloride,

rac-dimethylsilylene-bis[1-(2-ethyl-4-phenylindenyl)] zirconiumdichloride,

rac-dimethylsilyl-bis{1-[2-ethyl-4-(1-naphthyl)indenyl]} zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-ethyl-4-(9-phenanthryl)indenyl]} zirconiumdichloride,

rac-dimethylsilylene-bis[1-(2-n-propyl-4-phenylindenyl)] zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-n-propyl-4-(1-naphthyl)indenyl]} zirconiumdichloride,

rac-dimethylsilylene-bis{1-[2-n-propyl-4-(9-phenanthryl)indenyl]}zirconium dichloride, etc.

As the group 4 transition metal compounds (A2) and (A2′), two or moredifferent kinds of compounds can also be used.

Together with (A1) a group 4 transition metal compound represented bythe general formula [I] and (A2) a group 4 transition metal compoundrepresented by the general formula [II], in the polymerization catalystaccording to the present invention, compounds described in the presentapplicant's Japanese Patent Application Laid-Open No. 11-315109 andEP0874005A1 can be used without limitation as at least one compoundselected from (b-1) an organometallic compound, (b-2) an organoaluminumoxy compound, and (b-3) a compound reacting with the transition metalcompound (A1) or (A2) to form an ion pair.

The organometallic compound (b-1) is preferably an organoaluminumcompound, and one or more kinds thereof can be used in combination. Theorganoaluminum oxy compound (b-2) is preferably aluminoxane preparedfrom trialkyl aluminum or tricycloalkyl aluminum, more preferably anorganoaluminum oxy compound prepared from trimethyl aluminum ortriisobutyl aluminum. Such organoaluminum oxy compounds are used aloneor as a mixture of two or more thereof. Lewis acid, ionic compounds,borane compounds and carborane compounds described in Japanese PatentApplication Laid-Open No. 1-1501950, Japanese Patent ApplicationLaid-Open No.1-502036, Japanese Patent Application Laid-Open No.3-179005, Japanese Patent Application Laid-Open No.3-179006, JapanesePatent Application Laid-Open No. 3-207703, Japanese Patent ApplicationLaid-Open No. 3-207704 and U.S. Pat. No. 5,321,106, and furtherheteropoly compounds and isopoly compounds can be used withoutlimitation as the compound (b-3) which reacts with the transition metalcompound (A1) or (A2) to form an ion pair.

When the transition metal compound according to the present invention isused as a catalyst, an organoaluminum oxy compound (b-2′) such as methylaluminoxane can be simultaneously used as a co-catalyst component toexhibit very high polymerization activity on an olefin compound. Anionized ionic compound (b-3) such as triphenyl carbonium tetrakis(pentafluorophenyl) borate can be used as a co-catalyst component toproduce, with good activity, an olefin polymer having a very highmolecular weight.

In the olefin polymerization catalyst according to the presentinvention, the group 4 transition metal compounds (A1) and (A2), and (B)at least one compound selected from (b-1) an organometallic compound,(b-2) an organoaluminum oxy compound, and (b-3) a compound reacting withthe transition metal compounds (A1) and (A2) to form an ion pair, arecarried on a solid carrier (C) described below.

(C) Solid Carrier

The solid carrier (C) used in the present invention is an inorganic ororganic compound in the form of granular or particulate solid.

The inorganic compound is preferably a porous oxide, inorganic chloride,clay, clay mineral, or ion-exchangeable layered compound.

Specific examples of the porous oxide used include SiO₂, Al₂O₃, MgO,ZrO, TiO₂, B₂O₃, CaO, ZnO, BaO and ThO₂ or complexes or mixturescontaining them, for example natural or synthetic zeolite, SiO₂—MgO,SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃ and SiO₂—TiO₂—MgO. Amongthese, those based on SiO₂ and/or Al₂O₃ are preferable.

The above inorganic oxide may contain a small amount of carbonates,sulfates, nitrates and oxide components such as Na₂CO₃, K₂CO₃, CaCO₃,MgCO₃, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O,Li₂O etc.

Although the properties of such porous oxides are varied depending onthe type and process thereof, the particle diameter of the carrier usedpreferably in the present invention is 0.2 to 300 μm, preferably 1 to200 μm, the specific surface area thereof is 50 to 1200 m²/g, preferably100 to 1000 m²/g, and the void volume thereof is desirably in the rangeof 0.3 to 30 cm³/g. The carrier is used if necessary after baking at atemperature of 100 to 1000° C., preferably 150 to 700° C.

As the inorganic chloride, MgCl₂, MgBr₂, MnCl₂, MnBr₂ etc. are used. Theinorganic chloride may be used as it is or may be used after millingwith a ball mill, a vibration mill or the like. Fine particles of theinorganic chloride obtained by dissolving the inorganic chloride in asolvent such as alcohol and then precipitating it with a precipitatorcan also be used.

The clay used in the present invention is composed usually of claymineral as a major component. The ion-exchangeable layered compound usedin the present invention is a compound having a crystal structure inwhich faces constituted by ionic bonding etc. are layered in parallel byweak bonding force, and ions contained therein are exchangeable with oneanother. A majority of clay minerals are ion-exchangeable layeredcompounds. These clays, clay minerals and ion-exchangeable layeredcompounds are not limited to natural products, and artificiallysynthesized products can also be used.

The clays, clay minerals or ion-exchangeable layered compounds can beexemplified by clays, clay minerals, and ionic crystalline compoundshaving a layered crystal structure of hexagonal close packing type,antimony type, CdCl₂ type or CdI₂ type.

Such clays and clay mineral include kaolin, bentonite, kibushi clay,gairome clay, allophane, hisingerite, pyrophyllite, mica group,montmorillonite group, vermiculite, chlorite group, palygorskite,kaolinite, nacrite, dickite, halochite etc., and the ion-exchangeablelayered compounds include crystalline acidic salts of multivalentmetals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂, α-Zr(KPO₄)₂.3H₂O,α-Ti(HPO₄)₂, α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O, γ-Zr(HPO₄)₂,γ-Ti(HPO₄)₂, γ-Ti (NH₄PO₄)₂.H₂O etc.

Such clays, clay minerals or ion-exchangeable layered compounds arethose in which the volume of voids having a radius of 20 Å or more ispreferably 0.1 cc/g or more, more preferably 0.3 to 5 cc/g. The voidvolume measured herein is the volume of voids having a radius in therange of 20 to 3×10⁴ Å by porosimetry using a mercury porosimeter.

When a material in which the volume of voids having a radius of 20 Å ormore is less than 0.1 cc/g is used as a carrier, high polymerizationactivity tends to be hardly obtained.

The clays and clay minerals used in the present invention are preferablysubjected to chemical treatment. As chemical treatment, any treatmentsuch as surface treatment for removing impurities adhering to a surfaceand treatment for giving an influence to a crystal structure of clay canbe used. Specifically, the chemical treatment includes acid treatment,alkali treatment, salt treatment, organic material treatment etc. Theacid treatment not only removes impurities from a surface, but alsoincreases surface area by eluting cations such as Al, Fe, Mg etc. in acrystal structure. The alkali treatment brings about a change in a claystructure by destroying a crystal structure of clay. By the salttreatment or organic substance treatment, a surface area and a distancebetween layers can be changed by forming an ion complex, a molecularcomplex, an organic derivative etc.

The ion-exchangeable layered compound used in the present invention maybe a layered compound in such a state that the distance between layersis increased by exchanging exchangeable ions between the layers withother larger bulky ions by utilizing its ion exchangeability. Such bulkyions play a role as a pillar for supporting the layered structure, andis usually called a pillar. Such introduction of other substances intobetween layers in the layered compound is called intercalation. A guestcompound subjected to intercalation includes cationic inorganiccompounds such as TiCl₄ and ZrCl₄, metal alkoxides such as Ti(OR)₄,Zr(OR)₄, PO(OR)₃ and B(OR)₃ (where R is a hydrocarbon group or thelike), and metal hydroxide ions such as [Al₁₃O₄(OH)₂₄]⁷⁺, [Zr₄(OH)₁₄]²⁺and [Fe₃O(OCOCH₃)₆]⁺. These compounds are used alone or as a mixture oftwo or more thereof. For intercalation of these compounds, polymericproducts obtained by hydrolyzing metal alkoxides such as Si (OR)₄,Al(OR)₃ and Ge (OR)₄ (where R is a hydrocarbon group or the like) orcolloidal inorganic compounds such as SiO₂ can be coexistent. The pillarincludes oxides formed by thermal dehydration after intercalation of themetal hydroxide ions into between layers.

The clays, clay minerals and ion-exchangeable layered compounds used inthe present invention may be used as such, or may be used aftertreatment by a ball mill, sifting etc. These materials may be used afteraddition and adsorption of new water or after thermal dehydrationtreatment. These materials may be used alone or as a mixture of two ormore thereof.

Among these materials, clays or clay minerals are preferable, amongwhich montmorillonite, vermiculite, pectolite, taeniolite and syntheticmica are particularly preferable.

The organic compound includes granular or particulate solids having aparticle diameter in the range of 10 to 300 μm. Specific examplesinclude (co)polymers formed from C2 to C14 olefins such as ethylene,propylene, 1-butene and 4-methyl-1-pentene as major components,(co)polymers formed from vinyl cyclohexane and styrene as majorcomponents, and modified products thereof.

The olefin polymerization catalyst according to the present inventioncan, if necessary, contain a specific organic compound component (D)together with the transition metal compounds (A1) and (A2) and at leastone compound (B) selected from (b-1) an organometallic compound, (b-2)an organoaluminum oxy compound and (b-3) an ionized ionic compound. Asthe organic compound component, compounds described in Japanese PatentApplication Laid-Open No. 11-315109 and EP0874005A1, both of which werefiled by the present applicant, can be used without limitation.

In polymerization, the method of using the respective components and theorder of adding them are arbitrarily selected, and can be exemplified bythe following methods:

[1] a method wherein the catalyst component having the components (A1)and (B) carried on the carrier (C), and the catalyst component havingthe components (A2) and (B) carried on the carrier (C), are added in anarbitrary order to a polymerizer, and

[2] a method wherein the catalyst component having the components (A1),(A2) and (B) carried on the carrier (C) is added to a polymerizer.

In the method described in the above-mentioned [1], at least two of therespective catalyst components maybe previously contacted with oneanother.

The respective methods in the above-mentioned [1] and [ 2] wherein thecomponent (B) is carried, the component (B) not carried if necessary maybe added in an arbitrary order. In this case, the component (B) may bethe same or different.

The solid catalyst component having the components (A1), (A2) and (B)carried on the carrier (C) in the above-mentioned [1] and [2] may bepreliminarily polymerized with an olefin, and the catalyst component maybe carried on the preliminarily polymerized solid catalyst component.

Carrying the components (A1) and (B) onto the carrier (C) or carryingthe components (A2) and (B) on the carrier (C) in the above-mentioned[1] can be easily conducted according to a known method. Carrying thecomponents (A1), (A2) and (B) on the carrier (C) in the above-mentioned[2] is conducted preferably in the following manner.

One method is a method in which the components (A1) and (A2) arepreliminarily contacted with each other and then contacted with thecarrier (C) having the component (B) carried thereon, and another methodis a method in which the component (A1) [or the component (A2)] is firstcontacted with the carrier (C) having the component (B) carried thereonand then the component (A2) [or the component (A1)] is contacted withthe above carrier (C) having the component (A1) [or the component (A2)]and the component (B) carried thereon. The former method, that is, amethod in which the components (A1) and (A2) are preliminarily contactedwith each other and then contacted with the carrier (C) having thecomponent (B) carried thereon, is particularly preferable.

Specifically, the components (A1) and (A2) are dissolved in an arbitraryratio in an inert hydrocarbon solvent and then contacted in an inerthydrocarbon solvent with the carrier (C) having the component (B)carried thereon, to carry the components (A1), (A2) and (B) on thecarrier (C).

The inert hydrocarbon solvent used in carrying the components includes,for example, aliphatic hydrocarbons such as propane, butane, pentane,hexane, heptane, octane, decane, dodecane and kerosine, alicyclichydrocarbons such as cyclopentane, cyclohexane and methyl cyclopentane,aromatic hydrocarbons such as benzene, toluene and xylene, halogenatedhydrocarbons such as ethylene chloride, chlorobenzene anddichloromethane, or mixtures thereof. The preliminary contact time ofcomponent (A1) with component (A2) is usually 0 to 5 hours, preferably 0to 1 hour, more preferably 0 to 20 minutes, and thereafter, the time ofcontacting them with the carrier (C) having the component (B) carriedthereon is usually 0 to 24 hours, preferably 0 to 5 hours, morepreferably 0 to 2 hours. These carrying procedures are conducted usuallyat −50 to 200° C., preferably −50 to 50° C., more preferably 0 to 40° C.The components (A1) and (A2) can be arbitrarily determined depending onthe molecular weight and molecular weight distribution of polyolefindesired to be produced, and the molar ratio [(A1)/(A2)] of the component(A1) to the component (A2) can be determined from the olefinpolymerization activities of the components (A1) and (A2) respectively.[(A1)/(A2)] is usually 0.03 to 30, preferably 0.06 to 15.

The total transition metal atom (M) in the components (A1) and (A2)carried on the carrier (C) can be determined by inductively coupledplasma-emission spectrometry (ICP analysis).

The component (b-1) is used in such an amount that the molar ratio[(b-1)/M] of the component (b-1) to the total transition metal atom (M)in the components (A1) and (A2) becomes usually 0.01 to 100000,preferably 0.05 to 50000. The component (b-2) is used in such an amountthat the molar ratio [(b-2) /M] of aluminum atom in the component (b-2)to the total transition metal atom (M) in the components (A1) and (A2)becomes usually 10 to 500000, preferably 20 to 100000. The component(b-3) is used in such an amount that the molar ratio [(b-3)/M] of thecomponent (b-3) to the total transition metal atom (M) in the components(A1) and (A2) becomes usually 1 to 10, preferably 1 to 5.

When the component (B) is the component (b-1), the component (D) is usedin such an amount that the molar ratio [(D)/(b-1)] becomes usually 0.01to 10, preferably 0.1 to 5; when the component (B) is the component(b-2), the component (D) is used in such an amount that the molar ratio[(D)/(b-2)] becomes usually 0.001to 2, preferably 0.005 to 1; and whenthe component (B) is the component (b-3), the component (D) is used insuch an amount that the molar ratio (D) (b-3)] becomes usually 0.01 to10, preferably 0.1 to 5.

In the olefin polymerization method according to the present invention,an olefin polymer is obtained by polymerizing or copolymerizing olefinsin the presence of the polymerization catalyst described above.

The polymerization in the present invention can be carried out byliquid-phase polymerization such as solution polymerization orsuspension polymerization or by gaseous-phase polymerization.

Examples of inert hydrocarbon solvents used in the liquid-phasepolymerization include aliphatic hydrocarbons such as propane, butane,pentane, hexane, heptane, octane, decane, dodecane and kerosine;alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons such as benzene, toluene andxylene; halogenated hydrocarbons such as ethylene chloride,chlorobenzene and dichloromethane, or mixtures thereof, and olefinsthemselves can also be used as the solvent.

When the olefin polymerization catalyst described above is used inpolymerization of olefins, the components (A1) and (A2) are used usuallyin an amount of 10⁻¹² to 10⁻¹ mole, preferably 10⁻⁸ to 10⁻² mole, perliter of there action volume, and if necessary, the specific organiccompound component (D) can be contained.

The temperature at which an olefin is polymerized by the olefinpolymerization catalyst is usually in the range of −50 to +200° C.,preferably 0 to +170° C., more preferably +60 to +170° C. Thepolymerization pressure is usually normal pressures to 100 kg/cm²,preferably normal pressures to 50 kg/cm², and the polymerizationreaction can be carried out in a batch, semi-continuous or continuoussystem. Further, polymerization can be carried out in two or more stagesdifferent in reaction conditions.

The molecular weight of the obtained olefin polymer can be regulated byallowing hydrogen to be present in the polymerization system or bychanging the polymerization temperature. Further, the molecular weightcan be regulated by difference in the component (B) used.

The olefin which can be polymerized by the olefin polymerizationcatalyst is as described above, and if necessary, it is possible tosimultaneously use C3 to C30, preferably C5 to C20, cyclic olefins suchas cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,tetracyclododecene, etc.; polar monomers such as acrylic acid,methacrylic acid, fumaric acid, maleic anhydride, etc.; α,β-unsaturatedcarboxylate esters such as methyl acrylate, ethyl acrylate, methylmethacrylate, ethyl methacrylate, methacrylic acid, etc.; vinyl esterssuch as vinyl acetate, vinyl propionate, etc.; unsaturated glycidyl suchas glycidyl acrylate, glycidyl methacrylate, etc.; and halogenatedolefins such as vinyl fluoride, vinyl chloride, etc.

As the olefin, vinyl cyclohexane, diene, polyene etc. can also be used.As the olefin, an aromatic vinyl compound such as styrene etc. and afunctional group-containing styrene derivative such as divinyl benzeneetc. can also be simultaneously used.

The ethylene-based polymer particles thus obtained may be formed intopellets by the following methods.

(1) A method wherein the ethylene-based polymer particles and othercomponents added if necessary are blended mechanically by using anextruder, a kneader or the like and then cut into pieces ofpredetermined size.

(2) A method wherein the ethylene-based polymer and other componentsadded if necessary are dissolved in a suitable good solvent (forexample, a hydrocarbon solvent such as hexane, heptane, decane,cyclohexane, benzene, toluene and xylene) followed by removing thesolvent, and subsequently the residues are mechanically blended by anextruder, a kneader or the like and cut into pieces of predeterminedsize.

The ethylene-based polymer according to the present invention can becompounded if necessary with additives such as a weather abilitystabilizer, a heat stabilizer, an antistatic agent, a slip inhibitor, ananti-blocking agent, a haze inhibitor, a lubricant, a dye, a nucleatingagent, a plasticizer, an aging inhibitor, an HCl absorber and anantioxidant and a pigment such as carbon black, titanium oxide, titaniumyellow, phthalocyanine, isoindoline, a quinacridone compound, acondensed azo compound, ultramarine, cobalt blue etc. in such a rangethat the object of the present invention is not hindered.

The ethylene-based polymer according to the present invention can beformed into a blow-molded product, an inflation-molded product, acasting-molded product, an extrusion-laminated molded product, anextrusion-molded product such as a pipe or a special shape, afoam-molded product, an injection-molded product. The ethylene-basedpolymer can also be used in fibers, monofilaments, and nonwoven fabrics.These molded products include molded products (laminates etc.)containing a part consisting of the ethylene-based polymer and a partconsisting of another resin. The ethylene-based polymer may be the onecrosslinked in the molding process. To give excellent properties, theethylene-based polymer according to the present invention can bepreferably used in a blow-molded product or in an extrusion-moldedproduct such as a pipe or a special shape, among the molded productsdescribed above.

The ethylene-based polymer of the present invention can be formed byblow molding into a bottle container, an industrial chemical can, agasoline tank etc. These molded products include molded products(laminates etc.) containing a part consisting of the ethylene-basedpolymer and a part consisting of another resin. Alternatively, a singlelayer of the ethylene-based polymer can be formed into a molded product.

A general bleaching agent represented by a chlorine-based bleachingagent, or a surfactant, can also be preferably used in the polymersolution.

The ethylene-based polymer of the present invention can be formed into apipe or a pipe joint formed by injection molding. These molded productsinclude molded products (laminates etc.) containing a part consisting ofthe ethylene-based polymer and a part consisting of another resin.Alternatively, a single layer of the ethylene-based polymer can beformed into a molded product.

These molded products can be colored with a coloring matter such astitanium oxide and phthalocyanine. The molded product conferred withfunctions by adding additives such as an antioxidant and an antistaticagent can be used.

Hereinafter, the present invention is described in more detail byreference to the Examples, but the present invention is not limited tothe Examples.

In the Examples, the hexene content of the ethylene/hexene copolymer wasdetermined by using FT-IR (SHIMAZU FTIR-8200D) The transition metal atomconcentration and the A1 concentration in the solid component and thesolid catalyst component were determined by inductively coupledplasma-emission spectrometry (ICP analysis).

Intrinsic Viscosity ([η])

The intrinsic viscosity is a value measured at 135° C. in a decalinsolvent. That is, about 20 mg granulated pellets are dissolved in 15 mldecalin and specific viscosity η_(sp) measured in-an oil bath at 135° C.This decalin solution is diluted with additional 5 ml decalin solvent,and then specific viscosity η_(sp) is measured in the same manner asabove. This diluting procedure is repeated further twice, and the valueof η_(sp)/C upon extrapolation of concentration (C) to 0 is determinedas the intrinsic viscosity (see the following equation).[η]=lim(η_(sp) /C) (C→0)Density (d)

A sheet of 0.5 mm in thickness (spacer shape; 9 sheets of 45×45×0.5 mmfrom a plate of 240×240×0.5 mm) was formed at a pressure of 100 kg/cm²with a hydraulic heat press machine set at 190° C. manufactured byShinto Metal Industries, Ltd. and then cooled under compression at apressure of 100 kg/cm² with another hydraulic heat press machine set at20° C. manufactured by Shinto Metal Industries, Ltd., to prepare ameasurement sample. As a hot plate, an SUS plate of 5 mm in thicknesswas used. This press sheet was heat-treated at 120° C. for 1 hour, thencooled gradually linearly over 1 hour to room temperature, and measuredfor density in a density gradient tube.

Weight-Average Molecular Weight (Mw), Number-Average Molecular Weight(Mn), and Polymer Blend Ratio (BR) of Low-Molecular Component toHigh-Molecular Component

These were measured-in the following manner by using GPC-150Cmanufactured by Waters. As columns for separation, TSK gel GMH6-HT andTSK gel GMH6-HTL were used, and their column sizes were 7.5 mm in innerdiameter and 600 mm in length respectively, and the column temperaturewas 140° C., and o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.)was used as the mobile phase and transferred at 1.0 ml/min. with 0.025wt % BHT (Takeda Chemical Industries, Ltd.) as an antioxidant. Theconcentration of a sample was 0.1 wt %, and the volume of the sampleinjected was 500 μl, and a differential refractometer was used as thedetector. Standard polystyrene having a molecular weight of Mw<1,000 andMw>4×10⁶ was a product of Tosoh Corporation, and standard polystyrenehaving a molecular weight of 1,000≦Mw≦4×10⁶ was a product of PressureChemical. The molecular weight is a value determined using universalcalibration with PE as the standard.

Separation of Molecular-Weight Curve

A program was prepared by using a visual basic of Excel (registeredtrademark) 97 manufactured by Microsoft. Curves to be separated wereseparated into 2 curves different in molecular weight withlogarithmico-normal distribution by convergence calculation. A curvegenerated by re-synthesizing the 2 separated curves was compared withthe molecular-weight curve obtained actually in GPC, and calculation wasperformed while the initial value was changed such that the two curvesbecame almost identical. This calculation was performed with the log(molecular weight) divided at intervals of 0.02. The intensity wasstandardized such that the area of the actually obtained molecularweight curve and the area of the curve obtained by re-synthesizing the 2separated curves became 1, and the calculation of curve separation wasrepeated until a value obtained by dividing, with the actually obtainedintensity (height), the absolute value of a difference between theintensity (height) of the actually obtained molecular weight curve andthe intensity (height) of the re-synthesized curve at each molecularweight became 0.4 or less, preferably 0.2 or less, more preferably 0.1or less in the molecular-weight range of 10,000 to 1,000,000, and became0.2 or less, preferably 0.1 or less, in the maximum position of twoseparated peaks. The difference between the Mw/Mn of a peak separated atthe low-molecular weight side and the Mw/Mn of a peak separated at thehigh-molecular weight side shall be 1.5 or less. The polymer blend ratio(BR) of the low-molecular component to the high molecular component wascalculated according to the following equation:BR=S _(L) /S _(H)

S_(L): area at the low-molecular component side in GPC chart

S_(H): area at the high-molecular component side in GPC chart

Measurement of MFR

Melt flow rate is measured in the following manner. That is, an orificesatisfying dimensions prescribed in JIS K7210 was fit in an automaticMFR measuring meter (manufactured by Tester Sangyo) manufacturedaccording to JISK7210, and a barrel (sample inlet) was heated and keptat 190° C. 4 g sample was introduced into the barrel, and a piston wasfit therein, bubbles were removed, and the sample was pre-heated for6minutes. After preheating, the sample was extruded under a loading of2.16 kg or 21.6 kg, and the weight of the sample extruded per 10 minuteswas calculated as melt flow rate.

Measurement of MT

Melt tension (MT) is determined by measuring the stress upon stretchinga molten ethylene-based polymer at a constant speed. That is, themeasurement was conducted using a MT measuring machine manufactured byToyo Seiki Seisaku-sho, Ltd., under conditions where the resintemperature was 190° C., the extrusion speed was 15 mm/min., the take-upspeed was 7.85 m/min., the nozzle diameter was 2.09 mmφ, and the nozzlelength was 8 mm.

Measurement of Swell Ratio

Swell ratio is measured in the following manner. That is, a nozzlehaving a nozzle diameter (D₀) of 3.0 mmφ and a length (L) of 3 mm wasfit in Capillograph-IB manufactured by Toyo Seiki Seisaku-sho, Ltd., anda barrel (sample inlet) was heated and kept at 190° C. About 10 g samplewas introduced into the barrel, and a piston was fit therein, bubbleswere removed, and the sample was pre-heated for 6 minutes. Afterpreheating, the sample was extruded at each of shear speeds of 0.25,0.5, 1, 2.5, 5, 10 and 25 sec⁻¹, and the strand diameter (Di) below 15mm apart from an nozzle outlet was measured by a laser light. The ratioof the thus measured strand diameter (D_(i)) to the nozzle diameter (D₀)[SR_(i)=D_(i)/D₀] is determined.

From a curve obtained by plotting SR_(i) against each shear speed on asemi-logarithmic section paper, a value at a shear speed of 9.98 sec⁻¹is read as swell ratio.

Measurement of Activation Energy of Fluidization (Ea)

Ea is measured in the following manner. That is, measurement of meltviscoelasity is conducted in the measurement frequency range of 0.1rad/sec to 100 rad/sec at each of temperatures of 150° C., 190° C. and230° C. in a nitrogen atmosphere by using a stress rheometer SR-5000manufactured by TA Instrument. As a jig for giving shearing to resin, aparallel plate of 25 mm in diameter is used. From a fluidization curveobtained at each temperature, a master curve with 190° C. as a standardtemperature is prepared, and from the temperature dependence of itsshift factor a_(T), Ea is calculated according to the Arrhenius'equation: log a_(T)=(Ea/2.303R) [(1/T)−(1/T₀)] (R, gas constant; T,absolute temperature; T₀, standard temperature).

The group 4 transition metal compounds (A1) and (A2) used in theExamples and Comparative Examples were synthesized by the methoddescribed above.

[Preparation of Solid Component (E)]

30 g silica (manufactured by Asahi Glass Co., Ltd.) dried at 150° C. for5 hours in a nitrogen stream was suspended in 466 ml toluene, and then134.3 ml solution of methyl alumoxane (308 mmol/ml in terms of A1 atom)in toluene was added dropwise at 25° C. to the suspension over 30minutes. Thereafter, the mixture was heated to 114° C. over 30 minutesand reacted at this temperature for 4 hours. Thereafter, the temperatureof the reaction mixture was decreased to 60° C., and the supernatant wasremoved by decantation. The solid component thus obtained was washed 3times with toluene, and toluene was added thereto to prepare slurry ofthe solid component (E) in toluene. A part of the resulting solidcomponent (E) was collected to examine its concentration, indicatingthat the slurry concentration was 0.1189 g/ml and the A1 concentrationwas 0.8377 mmol/ml.

EXAMPLE 1

[Preparation of solid catalyst component (F)]

71.05 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 8.95 mlslurry of the solid component (E) in toluene (1.06 g in terms of solidscontent) prepared above. Then, 20.0 ml solution containing 0.0165 mmolcompound (1) below and 0.0135 mmol compound (2) below was added there todropwise over 15 minutes, and the mixture was reacted at roomtemperature for 1 hour. Thereafter, the supernatant was removed bydecantation, and the remaining solids were washed 3 times with heptane,followed by adding 100 ml heptane, to prepare slurry of the solidcatalyst component (F) in heptane. A part of the resulting slurry of thesolid catalyst component (F) in heptane was collected to examine itsconcentration, indicating that the Zr concentration was 0.000201mmol/ml, and the A1 concentration was 0.0615 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen, and the liquidphase and gaseous phase were saturated with ethylene. Thereafter, 3 ml1-hexene, 1.0 ml solution of triisobutyl aluminum (manufactured by TosohFinechem Corporation) in heptane (0.5 mmol/ml in terms of aluminumatom), and 0.746 ml solid catalyst component (F) (0.00015 mmol in termsof zirconium atom) were added thereto, heated to 80° C. and subjected topolymerization for 3 hours while a mixed gas of ethylene/hydrogen(hydrogen concentration: 0.06 mol %) was supplied such that the totalpressure became 8 kg/cm²-G. The polymerization was terminated by addinga small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/1-hexene copolymer was 28.5 g, and the polymerization activityper 1 mmol zirconium was 190 kg/mmol. The hexene content was 0.48 mol%., the [η] value thereof was 3.54 dl/g, and the Mw, Mw/Mn, and BRthereof were 235000, 15.25, and 53/47, respectively.

EXAMPLE 2

[Preparation of Solid Catalyst Component (G)]

35.52 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 4.48 mlslurry of the solid component (E) in toluene (0.533 g in terms of solidscontent) prepared above. Then, 10.0 ml solution containing 0.0128 mmolcompound (1) used in Example 1 above and 0.0022 mmol compound (3) belowwas added thereto dropwise over 15 minutes, and the mixture was reactedat room temperature for 1 hour. Thereafter, the supernatant was removedby decantation, and the remaining solids were washed 3 times withheptane, followed by adding 100 ml heptane, to prepare slurry of thesolid catalyst component (G) in heptane. A part of the resulting slurryof the solid catalyst component (G) in heptane was collected to examineits concentration, indicating that the Zr concentration was 0.000105mmol/ml, and the A1 concentration was 0.0328 mmol/ml.

[Polymerization]

500 ml n-heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 3 ml 1-hexene, 1.0 ml solution of triisobutyl aluminum(manufactured by Tosoh Finechem Corporation) in heptane (0.5 mmol/ml interms of aluminum atom), and 0.762 ml solid catalyst component (G)(0.00008 mmol in terms of zirconium atom) were added thereto, heated to80° C. and subjected to polymerization for 3 hours while a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.06 mol %) was supplied suchthat the total pressure became 8 kg/cm²-G. The polymerization wasterminated by adding a small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/1-hexene copolymer was 18.7 g, and the polymerization activityper 1 mmol zirconium was 234 kg/mmol. The hexene content was 0.32 mol %,the [η] value thereof was 3.39 dl/g, and the Mw, Mw/Mn, and BR thereofwere 240000, 15.91, and 54/46, respectively.

EXAMPLE 3

[Preparation of Solid Catalyst Component (H)]

35. 52 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 4.48 mlslurry of the solid component (E) in toluene (0.533 g in terms of solidscontent) prepared above. Then, 10.0 ml solution containing 0.0116 mmolcompound (4) below and 0.0034. mmol compound (3) used in Example 2 abovewas added thereto dropwise over 15 minutes, and the mixture was reactedat room temperature for 1 hour. Thereafter, the supernatant was removedby decantation, and the remaining solids were washed 3 times withheptane, followed by adding 100 ml heptane, to prepare slurry of thesolid catalyst component (H) in heptane. A part of the resulting slurryof the solid catalyst component (H) in heptane was collected to examineits concentration, indicating that the Zr concentration was 0.000110mmol/ml, and the A1 concentration was 0.0280 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 3 ml 1-hexene, 1.0 ml solution of triisobutyl aluminum(manufactured by Tosoh Finechem Corporation) in heptane (0.5 mmol/ml interms of aluminum atom), and 0.455 ml solid catalyst component (H)(0.00005 mmol in terms of zirconium atom) were added thereto, heated to80° C. and subjected to polymerization for 3 hours while a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.06 mol %) was supplied suchthat the total pressure became 8 kg/cm²-G. The polymerization wasterminated by adding a small amount of methanol.

The resulting polymer was,washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/1-hexene copolymer was 22.6 g, and the polymerization activityper 1 mmol zirconium was 452 kg/mmol. The hexene content was 0.67 mol %,the [η] value thereof was 3.89 dl/g, and the Mw, Mw/Mn., and BR thereofwere 207000, 18.64, and 56/44, respectively.

EXAMPLE 4

[Preparation of Solid Catalyst Component (J)]

35.52 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 4.48 mlslurry of the solid component (E) in toluene (0.533 g in terms of solidscontent) prepared above. Then, 10.0 ml solution containing 0.006 mmolcompound (4) used in Example 3 above and 0.009 mmol compound (3) used inExample 2 above was added thereto dropwise over 15 minutes, and themixture was reacted at room temperature for 1 hour. Thereafter, thesupernatant was removed by decantation, and the remaining solids werewashed 3 times with heptane, followed by adding 100 ml heptane, toprepare slurry of the solid catalyst component (J) in heptane. A part ofthe resulting slurry of the solid catalyst component (J) in heptane wascollected to examine its concentration, indicating that the Zrconcentration was 0.000121 mmol/ml, and the A1 concentration was 0.0307mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 3 ml 1-hexene, 1.0 ml solution of triisobutyl aluminum(manufactured by Tosoh Finechem Corporation) in heptane (0.5 mmol/ml interms of aluminum atom), and 0.207 ml solid catalyst component (J)(0.000025 mmol in terms of zirconium atom) were added thereto, heated to80° C. and subjected to polymerization for 3 hours while ethylene wassupplied such that the total pressure became 8 kg/cm²-G. Thepolymerization was terminated by adding a small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/1-hexene copolymer was 30.2 g, and the polymerization activityper 1 mmol zirconium was 1210 kg/mmol. The hexene content was 0.85 mol%, the [η] value thereof was 3.10 dl/g, and the Mw, Mw/Mn, and BRthereof were 337000, 12.39, and 41/59, respectively.

EXAMPLE 5

[Preparation of Solid Catalyst Component (K)]

35.52 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 4.48 mlslurry of the solid component (E) in toluene (0.533 g in terms of solidscontent) prepared above. Then, 10.0 ml solution containing 0.00975 mmolcompound (5) below and 0.00525 mmol compound (3) used in Example 2 abovewas added thereto dropwise over 15 minutes, and the mixture was reactedat room temperature for 1 hour. Thereafter, the supernatant was removedby decantation, and the remaining solids were washed 3 times withheptane, followed by adding 100 ml heptane, to prepare slurry of thesolid catalyst component (K) in heptane. A part of the resulting slurryof the solid catalyst component (K) in heptane was collected to examineits concentration, indicating that the Zr concentration was 0.000117mmol/ml, and the A1 concentration was 0.0321 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 3 ml 1-hexene, 1.0 ml solution of triisobutyl aluminum(manufactured by Tosoh Finechem Corporation) in heptane (0.5mmol/ml interms of aluminum atom), and 0.214 ml solid catalyst component (K)(0.000025 mmol in terms of zirconium atom) were added thereto, heated to80° C. and subjected to polymerization for 3 hours while a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.06 mol %) was supplied suchthat the total pressure became 8 kg/cm²-G. The polymerization wasterminated by adding a small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/hexene copolymer was 14.0 g, and the polymerization activityper 1 mmol zirconium was 560 kg/mmol. The hexene content was 0.60 mol %,the [η] value thereof was 4.01 dl/g, and the Mw, Mw/Mn, and BR thereofwere 189000, 12.68, and 43/57, respectively.

EXAMPLE 6

[Preparation of Solid Catalyst Component (L)]

35.52 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 4.48 mlslurry of the solid component (E) in toluene (0.533 g in terms of solidscontent) prepared above. Then, 10.0 ml solution containing 0.0105 mmolcompound (5) used in Example 5 above and 0.0045 mmol compound (6) belowwas added thereto dropwise over 15 minutes, and the mixture was reactedat room temperature for 1 hour. Thereafter, the supernatant was removedby decantation, and the remaining solids were washed 3 times withheptane, followed by adding 100 ml heptane, to prepare slurry of thesolid catalyst component (L) in heptane. A part of the resulting slurryof the solid catalyst component (L) in heptane was collected to examineits concentration, indicating that the Zr concentration was 0.000120mmol/ml, and the A1 concentration was 0.0324 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of I liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 3 ml 1-hexene, 1.0 ml solution of triisobutyl aluminum(manufactured by Tosoh Finechem Corporation) in heptane (0.5 mmol/ml interms of aluminum atom), and 0.208ml solid catalyst component (L)(0.000025 mmol in terms of zirconium atom) were added thereto, heated to80° C. and subjected to polymerization for 3 hours while a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.06 mol %) was supplied suchthat the total pressure became 8 kg/cm²-G. The polymerization wasterminated by adding a small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/hexene copolymer was 14.6 g, and the polymerization activityper 1 mmol zirconium was 584 kg/mmol. The hexene content was 0.55 mol %,the [η] value thereof was 4.34 dl/g, and the Mw, Mw/Mn, and B.R. thereofwere 234000, 24.67, and 41/59, respectively.

EXAMPLE 7

[Preparation of Solid Catalyst Component (M)]

35.52 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 4.48 mlslurry of the solid component (E) in toluene (0.533 g in terms of solidscontent) prepared above. Then, 10.0 ml solution containing 0.0105 mmolcompound (5) used in Example 5 above and 0.0045 mmol compound (7) belowwas added thereto dropwise over 15 minutes, and the mixture was reactedat room temperature for 1 hour. Thereafter, the supernatant was removedby decantation, and the remaining solids were washed 3 times withheptane, followed by adding 100 ml heptane, to prepare slurry of thesolid catalyst component (M) in heptane. A part of the resulting slurryof the solid catalyst component (M) in heptane was collected to examineits concentration, indicating that the Zr concentration was 0.000125mmol/ml, and the A1 concentration was 0.0317 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 3 ml 1-hexene, 1.0 ml solution of triisobutyl aluminum(manufactured by Tosoh Finechem Corporation) in heptane (0.5 mmol/ml interms of aluminum atom), and 0.200 ml solid catalyst component (M)(0.000025 mmol in terms of zirconium atom) were added thereto, heated to80° C. and subjected to polymerization for 3 hours while a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.06 mol %) was supplied suchthat the total pressure became 8 kg/cm²-G. The polymerization wasterminated by adding a small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/hexene copolymer was 16.0 g, and the polymerization activityper 1 mmol zirconium was 640 kg/mmol. The hexene content was 0.58 mol %,the [η] value thereof was 3.87 dl/g, and the Mw, Mw/Mn, and BR thereofwere 264000, 29.06, and 45/55, respectively.

COMPARATIVE EXAMPLE 1

[Preparation of Solid Catalyst Component (N)]

71.05 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 8.95 mlslurry of the solid component (E) in toluene (1.06 g in terms of solidscontent) prepared above. Then, 20.0 ml solution containing 0.03 mmolcompound (1) used in Example 1 above was added thereto dropwise over 15minutes, and the mixture was reacted at room temperature for 1 hour.Thereafter, the supernatant was removed by decantation, and theremaining solids were washed 3 times with heptane, followed by adding100 ml heptane, to prepare slurry of the solid catalyst component (N) inheptane. A part of the resulting slurry of the solid catalyst component(N) in heptane was collected to examine its concentration, indicatingthat the Zr concentration was 0.000270 mmol/ml, and the A1 concentrationwas 0.0689 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen at room temperature,and the liquid phase and gaseous phase were saturated with ethylene.Thereafter, 0.5 ml solution of triisobutyl aluminum (manufactured byTosoh Finechem Corporation) in heptane (0.5 mmol/ml in terms of aluminumatom) and 1.11 ml solid catalyst component (N) (0.003 mmol in terms ofzirconium atom) were added thereto, heated to 80° C. and subjected topolymerization for 107 minutes while a mixed gas of ethylene/hydrogen(hydrogen concentration: 2.53 mol %) was supplied such that the totalpressure became 8 kg/cm²-G. After the polymerization, the mixed gas ofethylene/hydrogen used was removed by depressurization and subsequentintroduction of nitrogen.

0.5 ml solution of triisobutyl aluminum (manufactured by Tosoh FinechemCorporation) in heptane (0.5 mmol/ml in terms of aluminum atom) and 5 ml1-hexene were introduced into this 1-L SUS autoclave, followed bysupplying a mixed gas of ethylene/hydrogen (hydrogen concentration:0.0305 mol %) such that the total pressure became 8 kg/cm²-G, and themixture was polymerized again at 80° C. for 17 minutes. Thepolymerization was terminated by adding a small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The amount of the resultingethylene/hexene copolymer was 100.4 g, and the polymerization activityper 1 mmol zirconium was 33 kg/mmol. The hexene content was 0.67 mol %,the [η] value thereof was 4.11 dl/g, and the Mw, Mw/Mn, and BR thereofwere 299000, 32.68, and 54/46, respectively.

EXAMPLE 8

[Preparation of Solid Component (O)]

30 g silica (manufactured by Asahi Glass Co., Ltd.) dried at 150° C. for5 hours in a nitrogen stream was suspended in 400 ml toluene, and then207.6 ml solution of methyl alumoxane (300 mmol/ml in terms of A1 atom)in toluene was added dropwise at 25° C. to the suspension over 30minutes. Thereafter, the mixture was heated to 114° C. over 30 minutesand reacted at this temperature for 4 hours. Thereafter, the temperatureof the reaction mixture was decreased to 60° C., and the supernatant wasremoved by decantation. The solid component thus obtained was washed 3times with toluene, and toluene was added thereto to prepare slurry ofthe solid component (O) in toluene. A part of the resulting solidcomponent (O) was collected to examine its concentration, indicatingthat the slurry concentration was 0.08123 g/ml and the Al concentrationwas 0.7339 mmol/ml.

[Preparation of Solid Catalyst Component (P)]

35.0 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 5.11 mlslurry of the solid component (O) in toluene (0.415 g in terms of solidscontent) prepared above. Then, 20.0 ml toluene solution containing0.0060 mmol compound (5) and 0.00909 mmol compound (6) used in Example 6above was added thereto dropwise over 15 minutes, and the mixture wasreacted at room temperature for 1 hour. Thereafter, the supernatant wasremoved by decantation, and the remaining solids were washed 3 timeswith heptane, followed by adding 100 ml heptane, to prepare slurry ofthe solid catalyst component (P) in heptane. A part of the resultingslurry of the solid catalyst component (P) in heptane was collected toexamine its concentration, indicating that the Zr concentration was0.000126mmol/ml, and the A1 concentration was 0.0347 mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen, and the liquidphase and gaseous phase were saturated with a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.101 mol %) . Thereafter, 3ml 1-hexene, 0.5 ml solution of triisobutyl aluminum (manufactured byTosoh Finechem Corporation) in heptane (1.0 mmol/ml in terms of aluminumatom), and 0.59 ml solid catalyst component (P) (0.000075 mmol in termsof zirconium atom) were added thereto, heated to 65° C. and subjected topolymerization for 3 hours while a mixed gas of ethylene/hydrogen(hydrogen concentration: 0.101 mol %) was supplied such that the totalpressure became 8 kg/cm²-G. The polymerization was terminated by addinga small amount of methanol.

The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours. The yield, polymerizationactivity per 1 mmol zirconium, hexene content, [η], Mw, Mw/Mn, andpolymer blend ratio (BR) of the resulting ethylene/hexene copolymer areshown in Table 1.

EXAMPLE 9

Polymerization was carried out in the same manner as in Example 8 exceptthat the hydrogen concentration of the mixed gas of ethylene andhydrogen was changed to 0.153 mol %. The resulting polymer was washedwith hexane and then dried under reduced pressure at 80° C. for 10hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 1.

EXAMPLE 10

Polymerization was carried out in the same manner as in Example 8 exceptthat the amount of the solid catalyst component (P) introduced waschanged to 0.79 ml (0.00010 mmol in terms of zirconium), the hydrogenconcentration of the mixed gas of ethylene and hydrogen was changed into0.064 mol %, and the polymerization temperature was changed to 60° C.The resulting polymer was washed with hexane and then dried underreduced pressure at 80° C. for 10 hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 1.

EXAMPLE 11

Polymerization was carried out in the same manner as in Example 8 exceptthat the amount of the solid catalyst component (P) introduced waschanged to 1.19 ml (0.00015 mmol in terms of zirconium), the amount of1-hexene was changed to 0 ml, and the hydrogen concentration of themixed gas of ethylene and hydrogen was changed into 0.062 mol %. Theresulting polymer was washed with hexane and then dried under reducedpressure at 80° C. for 10 hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 1.

EXAMPLE 12

Polymerization was carried out in the same manner as in Example 11except that the hydrogen concentration of the mixed gas of ethylene andhydrogen was changed to 0.153 mol %. The resulting polymer was washedwith hexane and then dried under reduced pressure at 80° C. for 10hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 1. TABLE 1 Poly- merization activity Hexene Yield (kg/content [η] Mw/ (g) mmol-Zr) (mol %) (dl/g) Mw Mn BR Example 8 28.8 3840.44 3.87 160000 18.2 52/48 Example 9 35.7 476 0.28 1.77 76800 8.8 60/40Example 10 42.9 429 0.22 1.82 82900 7.7 65/35 Example 11 67 446 — 2.07103500 8.7 56/44 Example 12 56 373 — 1.72 60900 8.8 54/46

EXAMPLE 13

[Preparation of Solid Catalyst Component (Q)]

35.0 ml toluene was introduced into a 300-ml glass flask flushedpreviously with nitrogen, and then charged under stirring with 5.11 mlslurry of the solid component (O) in toluene (0.415 g in terms of solidscontent) prepared above. Then, 20.0 ml toluene solution containing0.0060 mmol compound (8) below and 0.0090 mmol compound (6) used inExample 6 above was added thereto dropwise over 15 minutes, and themixture was reacted at room temperature for 1 hour. Thereafter, thesupernatant was removed by decantation, and the remaining solids werewashed 3 times with heptane, followed by adding 100 ml heptane, toprepare slurry of the solid catalyst component (Q) in heptane. A part ofthe resulting slurry of the solid catalyst component (Q) in heptane wascollected to examine its concentration, indicating that the Zrconcentration was 0.000120 mmol/ml, and the A1 concentration was 0.0318mmol/ml.

[Polymerization]

500 ml heptane was introduced into an SUS autoclave having an internalvolume of 1 liter purged sufficiently with nitrogen, and the liquidphase and gaseous phase were saturated with a mixed gas ofethylene/hydrogen (hydrogen concentration: 0.064 mol %). Thereafter, 3ml1-hexene, 0.5 ml solution of triisobutyl aluminum (manufactured by TosohFinechem Corporation) in heptane (1.0 mmol/ml in terms of aluminumatom), and 0.63 ml solid catalyst component (Q) (0.000075 mmol in termsof zirconium atom) were added thereto, heated to 65° C. and subjected topolymerization for 3 hours while a mixed gas of ethylene/hydrogen(hydrogen concentration: 0.064 mol %) was supplied such that the totalpressure became 8 kg/cm²-G. The polymerization was terminated by addinga small amount of methanol. The resulting polymer was washed with hexaneand then dried under reduced pressure at 80° C. for 10 hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 2.

EXAMPLE 14

Polymerization was carried out in the same manner as in Example 13except that the hydrogen concentration of the mixed gas of ethylene andhydrogen was changed to 0.101 mol %. The resulting polymer was washedwith hexane and then dried under reduced pressure at 80° C. for 10hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 2.

EXAMPLE 15

Polymerization was carried out in the same manner as in Example 13except that the hydrogen concentration of the mixed gas of ethylene andhydrogen was changed to 0.153 mol %. The resulting polymer was washedwith hexane and then dried under reduced pressure at 80° C. for 10hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 2.

EXAMPLE 16

Polymerization was carried out in the same manner as in Example 13except that the amount of the solid catalyst component (Q) introducedwas changed to 0.84 ml (0.00010 mmol in terms of zirconium), and thepolymerization temperature was changed to 60° C. The resulting polymerwas washed with hexane and then dried under reduced pressure at 80° C.for 10 hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 2.

EXAMPLE 17

Polymerization was carried out in the same manner as in Example 13except that the amount of the solid catalyst component (Q) introducedwas changed to 1.26 ml (0.00015 mmol in terms of zirconium), and theamount of 1-hexene was changed to 0 ml. The resulting polymer was washedwith hexane and then dried under reduced pressure at 80° C. for 10hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 2.

EXAMPLE 18

Polymerization was carried out in the same manner as in Example 16except that the hydrogen concentration of the mixed gas of ethylene andhydrogen was changed to 0.153 mol %. The resulting polymer was washedwith hexane and then dried under reduced pressure at 80° C. for 10hours.

The yield, polymerization activity per 1 mmol zirconium, hexene content,[η], Mw, Mw/Mn, and BR of the resulting ethylene/hexene copolymer areshown in Table 2. TABLE 2 Poly- merization activity Hexene Yield (kg/content [η] Mw/ (g) mmol-Zr) (mol %) (dl/g) Mw Mn BR Example 13 44.7 5970.24 3.04 151100 5 66/34 Example 14 30.9 413 0.22 3.04 142300 13.4 62/38Example 15 46.2 616 0.22 2.36 93800 10.4 65/35 Example 16 53.5 535 0.182.52 113100 4.1 64/36 Example 17 75.3 502 — 2.87 134400 4.6 58/42Example 18 53 353 — 2.22 104800 9.9 64/36Results of Evaluation of Physical Properties,

The physical properties of the ethylene-based polymers synthesized inthe Examples above are shown in Table 3. TABLE 3 MFR₂₀ MFR₂₀ DensitySwell Ea [η] Mw/ (g/10 min) (g/10 min) (kg/m³) MT g α¹⁾ ratio (KJ/mol)(dl/g) β²⁾ Mn Example 9 0.37 66 960 9 5.53 1.6 26 1.77 1.98 8.8 Example0.52 75 962 9 4.59 1.7 26 1.82 1.91 7.7 10 Example 0.29 29 965 13.5 6.321.6 25 2.07 2.46 8.7 11 Example 2.09 120 966 4 2.13 1.4 24 1.72 1.65 8.812 Example 0.03 5 952 32 22.02 1.7 24 3.04 3.49 5 13 Example 0.03 4 95030 22.02 1.7 25 3.04 3.58 13.4 14 Example 0.26 18 953 10.5 6.71 1.6 262.36 2.71 10.4 15 Example 0.25 15 953 11.5 6.86 1.7 25 2.52 2.81 4.1 16Example 0.13 9 957 14 9.83 1.7 26 2.87 3.14 4.6 17 Example 0.59 23 9606.5 4.28 1.8 23 2.22 2.57 9.9 18¹⁾α: 3.2 * MFR₂ ^(−0.55),²⁾β: 4.35 − 1.3log MFR₂₀

As can be seen from Table 3, the parameters of the ethylene-basedpolymers obtained in the Examples are within the ranges defined in theclaims.

The physical properties of conventionally known ethylene-based polymersin the Comparative Examples are shown in Tables 4 and 5. It is evidentthat-with respect to the known resins in the Comparative Examples andReference Examples, the relationship between MFR₂ and MT, and/or Eawhich is 30 KJ/mol or more, is outside of the claims.

COMPARATIVE EXAMPLE 1′ Ultzex UZ2510F (Brand Name) Manufactured byMitsui Chemicals, Inc. COMPARATIVE EXAMPLE 2 Ultzex UZ2520F (Brand Name)Manufactured by Mitsui Chemicals, Inc. COMPARATIVE EXAMPLE 3 HizexHZ8200B (Brand Name) Manufactured by Mitsui Chemicals, Inc. COMPARATIVEEXAMPLE 4 Evolue SP2520 (Brand Name) Manufactured by Mitsui Chemicals,Inc. COMPARATIVE EXAMPLE 5 Evolue SP2040 (Brand Name) Manufactured byMitsui Chemicals, Inc. COMPARATIVE EXAMPLE 6 Hizex 6008B (Brand Name)Manufactured by Mitsui Chemicals, Inc. COMPARATIVE EXAMPLE 7 MirasonF9725 (Brand Name) Manufactured by Mitsui Chemicals, Inc. COMPARATIVEEXAMPLE 8 Mirason M11 (Brand Name) Manufactured by Mitsui Chemicals,Inc.

TABLE 4 MFR₂₀ MFR₂₀ MT [η] Ea Brand name (g/10 min) (g/10 min) (g) α¹⁾(dl/g) β²⁾ (KJ/mol) Comparative UZ2510F 1.32 — 1.8 2.75 1.83 — 27Example 1′ Comparative UZ2520F 2.47 — 1.25 1.95 1.59 — 26 Example 2′Comparative HZ8200B 0.03 5.3 20.4 22.02 3.54 3.4  33 Example 3′Comparative SP2520 1.83 — 0.85 2.3 1.73 — 25 Example 4′ ComparativeSP2040 3.8 — 0.5 1.54 1.51 — 25 Example 5′ Comparative HZ6008B 0.36 35 85.61 2.45 2.34 30 Example 6′ Comparative F9725 1.14 — 8 2.98 1.17 — 42Example 7′ Comparative M11 7.91 — 3.6 1.03 1.1 — 46 Example 8′¹⁾α: 3.2 * MFR₂ ^(−0.55),²⁾β: 4.35 − 1.3log MFR₂₀

REFERENCE EXAMPLE 1 Hizex HZ9200B (Brand Name) Manufactured by MitsuiChemicals, Inc. REFERENCE EXAMPLE 2 Hizex HZ5300B (Brand Name)Manufactured by Mitsui Chemicals, Inc. REFERENCE EXAMPLE 3 MirasonMR102J (Brand Name) Manufactured by Mitsui Chemicals, Inc. REFERENCEEXAMPLE 4 Mirason MRFF999 (Brand Name) Manufactured by Mitsui Chemicals,Inc.

TABLE 5 MFR₂₀ [η] Ea (KJ/mol)/ Brand name (g/10 min) (dl/g) β¹⁾ (KL/mol)Reference HZ9200B 2.11 4.2 3.92 35 Example 1 Reference HZ5300B 48 2.42.16 32 Example 2 Reference MR102J 17 1.71 2.75 50 Example 3 ReferenceMRF999 43 1.19 2.26 43 Example 4¹⁾β: 4.35 − 1.3log MFR₂₀

INDUSTRIAL APPLICABILITY

The ethylene-based polymer of the present invention is excellent inmoldability to provide a molded product excellent in mechanical strengthand outward appearance. The ethylene-based polymer of the presentinvention, when used in blow-molded products and in extrusion-moldedproducts such as pipes and special shapes, gives excellentcharacteristics. By the olefin polymerization catalyst and thepolymerization method according to the present invention, theethylene-based polymer having the above-described excellent physicalproperties can be produced with high polymerization activity even insingle-stage polymerization.

1. An ethylene-based polymer which is a copolymer obtained from ethyleneand a C3 to C10 α-olefin and satisfies the following requirements (i),(ii), (iii) and (iv) simultaneously: (i) melt flow rate [MFR₂ (g/10min)] under a loading of 2.16 kg at 190° C. is in the range of 0.01 to10, (ii) melt tension [MT (g)] and the above melt flow rate [MFR₂ (g/10min)] satisfy the following relationship:MT≧3.2×MFR ₂ ^(−0.55) (iii) an activation energy [Ea] of fluidization isless than 30 (KJ/mol), and (iv) swell ratio is 1.36 or more.
 2. Theethylene-based polymer according to claim 1, which is obtained bycopolymerizing ethylene with a C3 to C10 α-olefin, in the presence of asolid catalyst component carried on (C) a solid carrier: (A1) a group 4transition metal compound represented by the general formula [I] below,(A2) a group 4 transition metal compound represented by the generalformula [II] below, and (B) at least one compound selected from: (b-1)an organometallic compound, (b-2) an organoaluminum oxy compound, and(b-3) a compound reacting with the transition metal compound (A1) or(A2) to form an ion pair,

where M represents a transition metal atom in the group 4 in theperiodic table, m represents an integer of 1 to 4, R represents abranched or linear aliphatic hydrocarbon group or an optionallysubstituted alicyclic hydrocarbon group, R² to R⁶ may be the same ordifferent and each represent a hydrogen atom, a halogen atom, ahydrocarbon group, a heterocyclic compound residue, an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group, two or more of which may be bound to one anotherto form a ring, and when m is 2, two of the groups represented by R² toR⁶ may be bound to each other provided that R¹'s shall not be bound toeach other, and n is a number satisfying the valence of M, X representsa hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or more, a plurality of groupsrepresented by X's may be the same or different, and a plurality ofgroups represented by X's may be bound to one another to form a ring,

where R⁷ to R²⁰ are selected from hydrogen, a hydrocarbon group and asilicon-containing group, and may be the same or different, adjacentsubstituents R⁷ to R²⁰ may be bound to each other to form a ring, M is agroup 4 transition metal atom, Y is a group 14 atom, Q may be selectedin the same or different combination from a halogen, a hydrocarbongroup, an anion ligand, and a neutral ligand capable of coordinationwith a lone pair of electrons, j is an integer of 1, to 4, at least oneof R¹⁹ and R²⁰ is an unsubstituted aryl group or a substituted arylgroup, and when both R¹⁹ and R²⁰ are either unsubstituted aryl groups orsubstituted aryl groups, R¹⁹ and R²⁰ may be the same or different.
 3. Asingle-layer or multi-layer blow-molded product comprising theethylene-based polymer according to claim 1 or
 2. 4. The single-layer ormulti-layer blow-molded product according to claim 3, wherein the moldedproduct is an oil drum, a 1000-L container, a gasoline tank, anindustrial chemical can or a bottle container.
 5. A single-layer ormulti-layer pipe or pipe joint comprising the ethylene-based polymeraccording to claim 1 or 2.